TW201842046A - Resin composition layer capable of obtaining a cured product excellent in base layer adhesion and anti-reflow properties - Google Patents

Abstract

An object of the present invention is to provide a resin composition layer or the like, which is capable of obtaining a cured product excellent in base layer adhesion and anti-reflow properties even when its thickness is small. To solve the problem, the resin composition layer of the present invention comprises a resin composition containing (A) an epoxy resin and (B) a curing agent, which is characterized in that the resin composition layer has a thickness of 15 micrometers or less, and when the resin composition layer is thermally cured at 100 DEG C for 30 minutes and is further thermally cured at 180 DEG C for 30 minutes, a cured product obtained therefrom has a permeability coefficient P of 1.2 cc/m2·mm<SP>-1</SP>·day·atom or more and 5 cc/m2mm<SP>-1</SP>·day·atom or less.

Description

Resin composition layer

The present invention relates to a resin composition layer. Furthermore, it relates to a resin sheet including the resin composition layer; a printed circuit board and a semiconductor device including an insulating layer formed of a cured product of the resin composition layer.

In recent years, in order to achieve miniaturization of electronic devices, further reductions in the thickness of printed circuit boards have been made, and in accordance with this, miniaturization of wiring circuits in inner substrates is being performed. For example, Patent Document 1 describes a resin sheet (adhesive film) including a support and a resin composition layer that can be used for fine wiring. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2014-36051

[Questions to be Solved by the Invention]

In order to achieve further miniaturization and thickness reduction of electronic devices, the inventors of the present invention have studied the resin composition layer of a thin resin sheet, but understand that the thin resin composition layer is suitable for use in build-up applications and is subject to semiconductor wafers. Due to the influence of the high temperature environment during installation, there is a possibility that sufficient adhesion cannot be ensured.

An object of the present invention is to provide a resin composition layer that can obtain a hardened material having excellent substrate adhesion and reflow resistance even with a small thickness; a resin sheet including the resin composition layer; and a structure formed by using the resin composition layer Printed circuit boards and semiconductor devices with insulating layers. [Means to solve the problem]

In order to achieve the subject of the present invention, the present inventors have conducted research and found that when the thickness of the resin composition layer is thin, oxygen in the hardened material of the resin composition layer is easily transmitted, and as a result, the adhesion is deteriorated. Therefore, by adjusting the transmission coefficient P of the hardened material of the resin composition layer to be within a specified range, it was found that even if the thickness of the resin composition layer is reduced, excellent substrate adhesion and reflow resistance can be obtained. The hardened product of the resin composition layer finally completes the present invention.

That is, the present invention includes the following. [1] A resin composition layer, which is a resin composition layer containing a resin composition containing (A) an epoxy resin and (B) a hardener, and is characterized in that the thickness of the resin composition layer is 15 μm or less. The transmittance coefficient P of the hardened material obtained by thermally curing the composition layer at 100 ° C for 30 minutes and further at 180 ° C for 30 minutes is 1.2cc / m ² · mm ^-1 · day · atom 5cc / m ² · mm ^-1 or more・ Day ・ atom or less. [2] The resin composition layer according to [1], which is used for wiring formation by a semi-additive method. [3] The resin composition layer according to [1] or [2], which contains (C) an inorganic filler. [4] The resin composition layer according to [3], wherein when the non-volatile content in the resin composition is 100% by mass, the content of the component (C) is 40% by mass or more and 80% by mass or less. [5] The resin composition layer according to [3] or [4], wherein the average particle diameter of the component (C) is 0.05 μm or more and 0.35 μm or less. [6] The resin composition layer according to any one of [1] to [5], wherein when the resin component is 100% by mass, the content of the component (B) is 20% by mass or less. [7] The resin composition layer according to any one of [1] to [6], wherein the component (B) contains an active ester-based hardener. [8] The resin composition layer according to [7], wherein when the resin component is 100% by mass, the content of the active ester-based hardener is 15% by mass or less. [9] The resin composition layer according to any one of [1] to [8], which contains (D) a thermoplastic resin. [10] The resin composition layer according to [9], wherein the weight average molecular weight of the component (D) is 38,000 or more. [11] The resin composition layer according to any one of [1] to [10], wherein the transmission coefficient P is 2cc / m ² · mm ^-1 · day · atom or more than 4cc / m ² · mm ^-1 · day ・ atom or less. [12] The resin composition layer according to any one of [1] to [11], which is used for forming an insulating layer of a printed circuit board. [13] The resin composition layer according to any one of [1] to [12], which is used for forming an interlayer insulating layer of a printed circuit board. [14] A resin sheet comprising a support and a resin composition layer according to any one of [1] to [13] provided on the support. [15] A printed circuit board comprising a first conductor layer, a second conductor layer, and an insulation layer formed between the first conductor layer and the second conductor layer, wherein the insulation layer is as follows The hardened | cured material of the resin composition layer in any one of [1]-[13]. [16] A semiconductor device comprising the printed circuit board according to [15]. [Effect of the invention]

According to the present invention, it is possible to provide a resin composition layer that can obtain a cured product having excellent substrate adhesion and reflow resistance even with a small thickness; a resin sheet including the resin composition layer; A printed circuit board and a semiconductor device with the formed insulating layer.

Hereinafter, the resin composition layer, the resin sheet, the printed circuit board, and the semiconductor device of the present invention will be described in detail.

The "resin component" refers to a component that removes the (C) inorganic filler described later among the non-volatile components constituting the resin composition.

[Resin composition layer] The resin composition layer of the present invention is a resin composition layer containing a resin composition containing (A) an epoxy resin and (B) a hardener, and is characterized in that the thickness of the resin composition layer is 15 μm or less The transmittance coefficient P of the cured product obtained by thermally curing the resin composition layer at 100 ° C for 30 minutes and further at 180 ° C for 30 minutes is 1.2cc / m ² · mm ^-1 · day · attom 5cc / m ² or more · Below mm ^-1・ day ・ atom. By adjusting the transmission coefficient P so that it is in the said range, even if the thickness of a resin composition layer is 15 micrometers or less, it can become a hardened | cured material excellent in the adhesiveness and reflow resistance of a substrate.

From the viewpoint of miniaturization and thinning, the thickness of the resin composition layer is 15 μm or less, preferably 13 μm or less, more preferably 10 μm or less, and even more preferably 8 μm or less. Although the lower limit of the thickness of the resin composition layer is not particularly limited, it may be generally 1 μm or more, 1.5 μm or more, 2 μm or more, and the like.

The resin composition layer is formed of a resin composition containing (A) an epoxy resin and (B) a hardener. Setting the transmission coefficient P within the above range can be achieved by adjusting each component contained in the resin composition. The resin composition may further contain additives such as (C) an inorganic filler, (D) a thermoplastic resin, (E) a hardening accelerator, (F) a flame retardant, and (G) an organic filler, if necessary. Hereinafter, each component contained in the resin composition of this invention is demonstrated in detail.

-(A) Epoxy resin-The fluorene resin composition system contains (A) an epoxy resin. Examples of the epoxy resin include bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, and bicyclic Pentadiene epoxy resin, phenol novolac epoxy resin, naphthol novolac epoxy resin, novolac epoxy resin, tert-butyl-catechol epoxy resin, naphthalene epoxy resin Resin, Naphthol type epoxy resin, Onion type epoxy resin, Glycidylamine type epoxy resin, Glycidyl ester type epoxy resin, Cresol novolac type epoxy resin, Biphenyl type epoxy resin, Wire Aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, epoxy resin containing spiral ring, cyclohexane epoxy resin, cyclohexane Dimethyl alcohol type epoxy resin, dnaphthyl ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin and the like. The epoxy resin may be used singly or in combination of two or more kinds.

The epoxy resin is preferably an epoxy resin having 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. Among them, the resin composition is preferably a combination of an epoxy resin that is liquid at a temperature of 20 ° C (hereinafter referred to as "liquid epoxy resin") and an epoxy resin that is solid at a temperature of 20 ° C (also referred to as a "epoxy resin") "Solid epoxy resin"). The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule, and more preferably an aromatic liquid epoxy resin having two or more epoxy groups in one molecule. Resin. The solid epoxy resin is preferably a solid epoxy resin having three or more epoxy groups in one molecule, and more preferably an aromatic solid epoxy resin having three or more epoxy groups in one molecule. Resin. In the present invention, an aromatic epoxy resin means an epoxy resin having an aromatic ring in its molecule.

The liquid epoxy resin is preferably a bisphenol A epoxy resin, a bisphenol F epoxy resin, a bisphenol AF epoxy resin, a naphthalene epoxy resin, a glycidyl ester epoxy resin, or a shrinking epoxy resin. Glycerylamine epoxy resin, phenol novolac epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexane epoxy resin, cyclohexanedimethanol epoxy resin, glycidylamine epoxy resin The epoxy resin and the epoxy resin having a butadiene structure are more preferably a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a cyclohexane type epoxy resin. Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene-type epoxy resin) manufactured by DIC Corporation, "828US", "jER828EL", and "825" manufactured by Mitsubishi Chemical Corporation. "," EPIKOTE828EL "(bisphenol A epoxy resin)," jER807 "," 1750 "(bisphenol F epoxy resin)," jER152 "(phenol novolac epoxy resin)," 630 "," 630 " "630LSD" (glycidylamine type epoxy resin), "ZX1059" (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., and manufactured by Nagase ChemteX Corporation "EX-721" (glycidyl ester type epoxy resin), "Celloxide 2021P" (alicyclic epoxy resin with ester skeleton) manufactured by Daicel, "PB-3600" (ring with butadiene structure) Oxygen resin), "ZX1658", "ZX1658GS" (liquid 1,4-glycidyl cyclohexane type epoxy resin) manufactured by Nippon Steel Chemical Co., Ltd., "630LSD" (glycidylamine) manufactured by Mitsubishi Chemical Corporation Type epoxy resin) and so on. These may be used alone or in combination of two or more.

As the solid epoxy resin, bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type 4-functional epoxy resin, cresol novolac type epoxy resin, and dicyclopentadiene type epoxy resin are preferable. Ginseng epoxy resin, naphthol epoxy resin, biphenyl epoxy resin, naphthyl ether epoxy resin, onion epoxy resin, bisphenol A epoxy resin, bisphenol AF ring Oxygen resin, tetraphenylethane type epoxy resin, more preferably bixylenol type epoxy resin, naphthalene type epoxy resin, bisphenol AF type epoxy resin, and naphthyl ether type epoxy resin. Specific examples of the solid epoxy resin include "HP4032H" (naphthalene-type epoxy resin), "HP-4700", "HP-4710" (naphthalene-type 4-functional epoxy resin), and "N" manufactured by DIC Corporation. -690 "(cresol novolac type epoxy resin)," N-695 "(cresol novolac type epoxy resin)," HP-7200 "(dicyclopentadiene type epoxy resin)," HP-7200HH "," HP-7200H "," EXA-7311 "," EXA-7311-G3 "," EXA-7311-G4 "," EXA-7311-G4S "," HP6000 "(dnaphthyl ether type epoxy resin ), "EPPN-502H" (ginseng phenol type epoxy resin), "NC7000L" (naphthol novolac type epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" manufactured by Nippon Kayaku Co., Ltd. "(Biphenyl type epoxy resin)," ESN475V "(naphthalene type epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.," ESN485 "(naphthol novolac type epoxy resin)," YX4000H manufactured by Mitsubishi Chemical "," YX4000 "," YL6121 "(biphenyl epoxy resin)," YX4000HK "(bixylenol epoxy resin)," YX8800 "(green onion epoxy resin), Osaka Gas Chemicals Corporation" PG-100 "CG-500", "YL7760" (bisphenol AF type epoxy resin), "YL7800" (type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "jER1010" (solid bisphenol A) manufactured by Mitsubishi Chemical Corporation Type epoxy resin), "jER1031S" (tetraphenylethane type epoxy resin), etc. These may be used alone or in combination of two or more.

When the liquid epoxy resin and the solid epoxy resin are used as the component (A), the quantity ratio (liquid epoxy resin: solid epoxy resin) is preferably 1: 1 to 1:20 in terms of quality. Range. By setting the ratio of the amount of the liquid epoxy resin to the solid epoxy resin within this range, i) is obtained when it is used in the form of a resin sheet to impart moderate adhesion, ii) it is obtained when used in the form of a resin sheet Sufficient flexibility, improved operability, and iii) the effect of obtaining a hardened product having sufficient breaking strength and the like. From the viewpoint of the effects of i) to iii), the mass ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is more preferably 1: The range is from 2 to 1:10, and more preferably from 1: 5 to 1:10.

The content of the component (A) in the resin composition is preferably 10% by mass or more when the resin component is set to 100% by mass from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. It is preferably at least 20% by mass, and even more preferably at least 30% by mass. Although the upper limit of the content of the epoxy resin is not particularly limited as long as the effects of the present invention can be exhibited, it is preferably 60% by mass or less, more preferably 55% by mass or less, 50% by mass or less, or 45% by mass.

The epoxy group equivalent of the component (A) is preferably 50 to 5000, more preferably 50 to 3000, even more preferably 80 to 2000, and still more preferably 110 to 1,000. By setting it as this range, the crosslinking density of hardened | cured material becomes sufficient, and the insulating layer with small surface roughness can be brought. The epoxy equivalent can be measured in accordance with JIS K7236, and is the mass of a resin containing one equivalent of an epoxy group.

The weight average molecular weight of the component (A) is preferably 100 to 5000, more preferably 250 to 3000, and even more preferably 400 to 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) Hardener- The resin composition system contains (B) a hardener. The component (B) is not particularly limited as long as it has a function of curing the component (A). Examples include a phenol-based hardener, a naphthol-based hardener, an active ester-based hardener, and a benzoxazine-based hardener. Agents, cyanate-based hardeners and carbodiimide-based hardeners. The hardener can be used alone or in combination of two or more.

As the phenol-based hardener and naphthol-based hardener, from the viewpoints of heat resistance and water resistance, a phenol-based hardener having a novolac structure or a naphthol-based hardener having a novolac structure is preferred. From the standpoint of adhesion with the conductor layer, a nitrogen-containing phenol-based hardener is preferred, and a phenol-based hardener containing a triazine skeleton is more preferred.

Specific examples of the phenol-based hardener and naphthol-based hardener include, for example, "MEH-7700", "MEH-7810", "MEH-7851", and "NHN" manufactured by Nippon Kayakusei Corporation. , "CBN", "GPH", "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V", "SN375", " "SN395", "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500", etc. manufactured by DIC Corporation.

Although the active ester-based hardener is not particularly limited, it is generally preferred to use phenol esters, thiophenol esters, N-hydroxyamine esters, heterocyclic hydroxy esters, etc. in one molecule. A compound having two or more highly reactive ester groups. The active ester-based hardener is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. Especially from the viewpoint of improving heat resistance, an active ester-based hardener obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester-based hardener obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. hardener. 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. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, and methylation. Bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxy Naphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, resorcinol, benzenetriol, dicyclopentadiene-type diphenol compound, phenol Novolac, etc. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol into one molecule of dicyclopentadiene.

Specifically, an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetophenate of a novolac, and a benzamidine containing a novolac Among the active ester compounds of the base compound, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene-type diphenol structure are more preferred. The "dicyclopentadiene-type diphenol structure" refers to a divalent structural unit composed of phenylene-dicyclopentyl-phenylene.

As a commercially available product of the active ester-based hardener, examples of the active ester compound containing a dicyclopentadiene-type diphenol structure include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC -8000H-65TM "," EXB-8000L-65TM "," EXB-8150-65T "(manufactured by DIC Corporation), as the active ester compound containing a naphthalene structure," EXB9416-70BK "(manufactured by DIC Corporation) can be cited as As an active ester compound containing an acetic acid compound of a phenol novolac, "DC808" (manufactured by Mitsubishi Chemical Corporation), and as an active ester compound containing a benzoic acid compound of a phenol novolac, "YLH1026" (Mitsubishi Chemical Corporation) (Manufactured), as the active ester-based hardener that is the acetic acid compound of phenol novolac, "DC808" (manufactured by Mitsubishi Chemical Corporation), and as the active ester-based hardener that is the benzoyl compound of phenol novolac, " "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation), and the like.

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

Examples of the cyanate-based curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), and 4,4 ' -Methylenebis (2,6-dimethylphenylcyanate), 4,4'-ethylenediphenyldicyanate, hexafluorobisphenol A dicyanate, 2,2- Bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5-dimethylphenyl) methane, 1, 3-bis (4-cyanatephenyl-1- (methylethylene)) benzene, bis (4-cyanatephenyl) sulfide, and bis (4-cyanatephenyl) ether Polyfunctional cyanate resins derived from bifunctional cyanate resins, phenol novolacs, cresol novolacs, etc., and prepolymers of which some of these cyanate resins are triazinated. Specific examples of the cyanate-based curing agent include "PT30" and "PT60" (phenol novolac-type polyfunctional cyanate resin) and "ULL-950S" (polyfunctional cyanate resin) manufactured by Lonza Japan. ), "BA230", "BA230S75" (prepolymers in which part or all of the bisphenol A dicyanate becomes a triazinated terpolymer) and the like.

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

The ratio of the amount of the epoxy resin to the hardener is a ratio of [total number of epoxy groups of the epoxy resin]: [total number of reactive groups of the hardener], preferably in a range of 1: 0.01 to 1: 2, and more It is preferably 1: 0.05 to 1: 1.5, and even more preferably 1: 0.1 to 1: 1. Here, the reactive group of the hardener is an active hydroxyl group, an active ester group, and the like, and varies depending on the type of the hardener. In addition, the total number of epoxy groups of an epoxy resin is a total value obtained by dividing the solid content of each epoxy resin by an epoxy group equivalent value for all epoxy resins. The total count is a value obtained by dividing the solid content of each hardener by the value of the reactive group equivalent for all the hardeners. By setting the amount ratio of the epoxy resin to the hardener within this range, the heat resistance of the hardened product of the resin composition layer is further improved.

In one embodiment, the resin composition includes the aforementioned epoxy resin and hardener. The resin composition preferably comprises a mixture of a liquid epoxy resin and a solid epoxy resin as (A) an epoxy resin, and (B) a hardener selected from a phenol-based hardener, a naphthol-based hardener, One or more of the group consisting of an active ester-based hardener and a cyanate-based hardener. As the (A) epoxy resin, the quality of the mixture of the liquid epoxy resin and the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is preferably 1: 0.1 to 1:20, and more preferably 1: 1 to 1:10, and more preferably 1: 5 to 1: 8. (B) The hardener is preferably one or more selected from the group consisting of a phenol-based hardener, a naphthol-based hardener, an active ester-based hardener, and a cyanate-based hardener, and more preferably One or more selected from the group consisting of a phenol-based hardener and an active ester-based hardener.

As (B) component, it is preferable to contain an active ester hardening | curing agent from a viewpoint of improving chemical resistance. The content of the active ester-based hardener is from the viewpoint of making it easy to adjust the transmission coefficient P within a specified range. When the resin component is 100% by mass, it is preferably 15% by mass or less, and more preferably 14% by mass. Hereinafter, it is more preferably 13% by mass or less. The lower limit is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 8% by mass or more.

The content ratio of the active ester hardener based on the entire (B) component is 100% by mass, preferably 40% by mass or more, more preferably 50% by mass or more, and still more preferably 60% by mass relative to the (B) component. %the above. The upper limit is preferably 75% by mass or less, more preferably 73% by mass or less, and even more preferably 70% by mass or less. By including the active ester hardener in such a range, it becomes easy to adjust the transmission coefficient P within a predetermined range.

When the content of the component (B) is 100% by mass, the content is preferably 20% by mass or less, more preferably 19% by mass or less, and still more preferably 18% by mass or less. The lower limit is preferably 1% by mass or more, even more preferably 5% by mass or more, and even more preferably 8% by mass or more. By setting the content of the component (B) within this range, the adhesion of the substrate can be effectively improved.

-(C) Inorganic Filler-(1) In one embodiment, the resin composition may contain an inorganic filler. Although the material of the inorganic filler is not particularly limited, examples thereof include silicon dioxide, aluminum oxide, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, Gibbsite, 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, zirconia, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium phosphate and zirconium phosphate. Among these, it is particularly suitable for silicon dioxide. Examples of the silicon dioxide include amorphous silicon dioxide, fused silicon dioxide, crystalline silicon dioxide, synthetic silicon dioxide, and hollow silicon dioxide. The silicon dioxide is preferably spherical silicon dioxide. The inorganic fillers may be used alone or in combination of two or more.

The average particle diameter of the inorganic filler is preferably 0.35 μm or less, more preferably 0.3 μm or less, and even more preferably from the viewpoint of increasing the surface area of the inorganic filler and adjusting the transmission coefficient P within a specified range. 0.25 μm or less, 0.2 μm or less, 1.5 μm or less, or 1 μm or less. The lower limit of the average particle diameter is preferably 0.05 μm or more, more preferably 0.06 μm or more, and still more preferably 0.07 μm or more. The upper limit of the average particle diameter is a commercially available product of an inorganic filler having such an average particle diameter, and examples thereof include "UFP-30" manufactured by Denki Kagaku Kogyo.

The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis by a laser diffraction scattering particle size distribution measurement device, and the median diameter can be determined as the average particle diameter. As the measurement sample, an inorganic filler is preferably dispersed in methyl ethyl ketone by ultrasonic waves. As the laser diffraction scattering type particle size distribution measuring device, "LA-500" manufactured by Horiba, Ltd., and "SALD-2200" manufactured by Shimadzu Corporation can be used.

The specific surface area of the inorganic filler is preferably 15 m ² / g or more, more preferably 20 m ² / g or more, and even more preferably 25 m ² / g or more from the viewpoint of adjusting the transmission coefficient P within a specified range. . The upper limit of the specific surface area is preferably 60 m ² / g or less, more preferably 50 m ² / g or less, and even more preferably 40 m ² / g or less. The specific surface area of the inorganic filler can be measured using, for example, a BET automatic specific surface area measuring device. More specifically, the specific surface area is obtained by using a specific surface area measuring device (Macsorb HM-1210, manufactured by Mountech Co., Ltd.) to adsorb nitrogen on the surface of a sample according to the BET method, and calculate the specific surface area using the BET multipoint method.

From the viewpoint of improving moisture resistance and dispersibility, the inorganic filler is preferably a fluorine-containing silane coupling agent, an amine-based silane coupling agent, an epoxy-based silane coupling agent, a mercaptosilane-based coupling agent, or a silane-based coupling agent. One or more surface treatment agents such as a coupling agent, an alkoxysilane compound, an organic silazane compound, and a titanate-based coupling agent are particularly preferably treated with an aminosilane coupling agent. Examples of commercially available surface treatment agents include "KBM403" (3-glycidyloxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd. and "KBM803" (3-mercaptopropyltrimethyl) manufactured by Shin-Etsu Chemical Industry Co., Ltd. Oxysilane), "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxy) manufactured by Shin-Etsu Chemical Industry Co., Ltd. Silane), Shin-Etsu Chemical Industry Co., Ltd. "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical Industry Co., Ltd. "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Industry Co., Ltd. "KBM-4803" (Long-chain epoxy-based silane coupling agent), "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

According to the degree of surface treatment of the surface treatment agent, from the viewpoint of improving the dispersibility of the inorganic filler, the surface treatment of 0.2 to 5 parts by mass of the surface treatment agent is better than 100 parts by mass of the component (C) The surface treatment is more preferably 0.2 to 3 parts by mass, and the surface treatment is more preferably 0.3 to 2 parts by mass.

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

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

When the resin composition contains the (C) component, the content of the inorganic filler is preferably from the viewpoint of adjusting the transmission coefficient P within a specified range. When the nonvolatile content in the resin composition is set to 100% by mass, it is preferable. It is 40% by mass or more, more preferably 45% by mass or more, and even more preferably 50% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 70% by mass or less, and still more preferably 60% by mass from the viewpoint of improving the insulation performance, adjusting the physical property balance of the resin composition layer, and improving the adhesion of the substrate. Or less than 55% by mass.

-(D) Thermoplastic resin-(1) In one embodiment, the resin composition may contain (D) a thermoplastic resin. Examples of the thermoplastic resin include a phenoxy resin, a polyvinyl acetal resin, a polyolefin resin, a polybutadiene resin, a polyimide resin, a polyimide resin, a polyetherimide resin, and a polyimide resin. A fluorene resin, a polyether fluorene resin, a polyphenylene ether resin, a polycarbonate resin, a polyetheretherketone resin, a polyester resin, and the like are preferably a phenoxy resin. The thermoplastic resin may be used singly or in combination of two or more kinds.

From the viewpoint of reducing the transmission coefficient P, the weight average molecular weight in terms of polystyrene of the thermoplastic resin is preferably 38,000 or more, more preferably 40,000 or more, and even more preferably 42,000 or more. The upper limit is preferably 100,000 or less, more preferably 70,000 or less, and even more preferably 60,000 or less. The polystyrene equivalent weight average molecular weight of the thermoplastic resin is measured by a gel permeation chromatography (GPC) method. Specifically, as a weight average molecular weight of a polystyrene conversion of a thermoplastic resin, LC-9A / RID-6A manufactured by Shimadzu Corporation can be used as a measuring device, and Shodex K-800P / K-804L / K-804L manufactured by Showa Denko Corporation can be used. As the column, chloroform was used as the movement equalizer. The column temperature was measured at 40 ° C and calculated using a calibration curve of standard polystyrene.

Examples of the phenoxy resin include those selected from the group consisting of a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a novolac skeleton, a biphenyl skeleton, a fluorene skeleton, and a dicyclopentadiene skeleton. Phenoxy resin with one or more skeletons in the group consisting of norbornene skeleton, naphthalene skeleton, onion skeleton, adamantane skeleton, terpene skeleton, and 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 resin may be used alone or in combination of two or more. Specific examples of the phenoxy resin include "1256" and "4250" (both are phenoxy resins containing a bisphenol A skeleton) and "YX8100" (phenoxy containing bisphenol S skeletons) manufactured by Mitsubishi Chemical Corporation. Base resin) and "YX6954" (phenoxy resin containing a bisphenol acetophenone skeleton). Other examples include "FX280" and "FX293" manufactured by Nippon Steel & Sumitomo Chemical Corporation, and "YL7500BH30" manufactured by Mitsubishi Chemical Corporation. , "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7482", etc.

Examples of the polyvinyl acetal resin include a polyethylene methylal resin and a polyethylene butyral resin, and a polyvinyl butyral resin is preferred. Specific examples of the polyvinyl acetal resin include, for example, "Electrochemical butyral 4000-2", "Electrochemical butyral 5000-A", "Electrochemical butyral 6000-C", and "Electrochemical butyral 6000-EP" manufactured by Denka Kogyo Co., Ltd. , S-Lec BH series, BX series (such as BX-5Z), KS series (such as KS-1), BL series, BM series, etc. manufactured by Sekisui Chemical Industry Company.

Specific examples of the polyimide resin include "RIKACOAT SN20" and "RIKACOAT PN20" manufactured by Nippon Rika Chemical Co., Ltd. Specific examples of the polyfluorene imine resin include linear polyfluorene imide obtained by reacting a bifunctional hydroxyl-terminated polybutadiene, a diisocyanate compound, and a quaternary acid anhydride (Japanese Patent Laid-Open No. 2006-37083). Polyimide described in the publication), polyimide containing a polysiloxane skeleton (polyimide described in JP 2002-12667 and JP 2000-319386, etc.) Quality polyimide.

Specific examples of the polyamidamine / imide resin include "Vylomax HR11NN" and "Vylomax HR16NN" manufactured by Toyobo Corporation. Specific examples of the polyimide resin include modified polyimide resins such as "KS9100" and "KS9300" (polysiloxane imine containing a polysiloxane skeleton) manufactured by Hitachi Chemical Industries, Ltd. Amine imine.

Specific examples of the polyether fluorene resin include "PES5003P" manufactured by Sumitomo Chemical Co., and the like. As a specific example of the polyphenylene ether resin, oligophenylene ether / styrene resin "OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Co., Ltd. can be cited.

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

Among these, as the thermoplastic resin, a phenoxy resin and a polyvinyl acetal resin are preferable. Accordingly, in a suitable embodiment, the thermoplastic resin includes one or more members selected from the group consisting of a phenoxy resin and a polyvinyl acetal resin. Among them, as the thermoplastic resin, a phenoxy resin is preferred, and a phenoxy resin having a weight average molecular weight of 40,000 or more is particularly preferred. By using a phenoxy resin having a weight average molecular weight of 40,000 or more, the transmission coefficient P is reduced, and the surface roughness can be stably formed even if the insulating layer is thinned.

When the resin composition contains a thermoplastic resin, when the content of the thermoplastic resin is 100% by mass, the content is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more. The upper limit is preferably 5 mass% or less, more preferably 3 mass% or less, and even more preferably 2 mass% or less. By setting the content of the (D) component within this range, the transmission coefficient P is reduced, and even if the insulating layer becomes thin, the surface roughness can be formed stably.

-(E) Hardening accelerator-(1) In one embodiment, the resin composition may contain (E) a hardening accelerator. Examples of the hardening accelerator include phosphorus-based hardening accelerators, amine-based hardening accelerators, imidazole-based hardening accelerators, guanidine-based hardening accelerators, and metal-based hardening accelerators, and phosphorus-based hardening accelerators and amine-based hardening accelerators are preferred Hardening accelerator, imidazole-based hardening accelerator, metal-based hardening accelerator, more preferably amine-based hardening accelerator, imidazole-based hardening accelerator, and metal-based hardening accelerator. A hardening accelerator can be used individually by 1 type or in combination of 2 or more types.

Examples of the phosphorus-based hardening accelerator include triphenylphosphine, osmium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, etc., preferably triphenylphosphine, tetrabutylphosphonium Decanoate.

Examples of the amine-based hardening accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, and 2,4,6-, (Dimethylaminomethyl) phenol, 1,8-diazabicyclo (5,4,0) -undecene, etc., preferably 4-dimethylaminopyridine, 1,8-bis Azabicyclo (5,4,0) -undecene.

Examples of the imidazole-based hardening accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methyl Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl 4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2- Phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamine -6- [2'-undecylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methyl Imidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine Cyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethyl Imidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzo Addition of imidazole compounds such as azole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, and the addition of an imidazole compound to an epoxy resin Is preferably 2-ethyl-4-methylimidazole or 1-benzyl-2-phenylimidazole.

A commercially available product can be used as the imidazole-based hardening accelerator, and examples thereof include "P200-H50" manufactured by Mitsubishi Chemical Corporation.

Examples of the guanidine-based hardening accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, and 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-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1- (o-tolyl) biguanide, etc., preferably It is dicyandiamide, 1,5,7-triazabicyclo [4.4.0] dec-5-ene.

Examples of the metal-based hardening accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include organocobalt complexes such as cobalt (II) acetopyruvate, cobalt (III) ethidium pyruvate, and organocopper complexes such as copper (II) acetopyruvate. Compounds, organic zinc complexes such as zinc (II) acetonate, organic iron complexes such as iron (III) acetonate, nickel organic complexes of nickel (II) acetonate , Organic manganese complexes such as manganese (II) acetamidine pyruvate and the like. Examples of the organic metal salt include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

When the resin composition contains a hardening accelerator, when the content of the hardening accelerator is 100% by mass of the resin component, it is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and still more preferably 0.1% by mass or more. The upper limit is preferably 3% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less. By setting the content of the hardening accelerator within this range, it becomes easy to improve the adhesion of the substrate.

-(F) Flame Retardant-(1) In one embodiment, the resin composition may contain (F) a flame retardant. Examples of the flame retardant include an organic phosphorus-based flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a polysiloxane flame retardant, and a metal hydroxide. The flame retardant can be used alone or in combination of two or more.

As the flame retardant, a commercially available product can be used, and examples thereof include "HCA-HQ" manufactured by Sanko Corporation, and "PX-200" manufactured by Daiba Chemical Industries. As the flame retardant, those which are difficult to hydrolyze are preferred, for example, 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxidation is preferred. Things.

When the resin composition contains a flame retardant, when the nonvolatile content in the resin composition is set to 100% by mass, the content of the flame retardant is preferably 0.5% to 20% by mass, and more preferably 0.5% to 15% by mass. %, More preferably 0.5% to 10% by mass.

-(G) Organic Filler-(1) In one embodiment, the resin composition may contain (G) an organic filler. By containing (G) component, the tensile fracture strength of the hardened | cured material of the resin composition layer of a resin sheet can be improved. As the organic filler, any organic filler used when forming an insulating layer of a printed circuit board can be used, and examples thereof include rubber particles, polyamide fine particles, and polysiloxane particles.

Commercially available rubber particles can be used, and examples thereof include "EXL2655" manufactured by Dow Chemical Japan, "AC3401N" manufactured by Aika Industries, and "AC3816N".

When the resin composition contains an organic filler, when the non-volatile content in the resin composition is set to 100% by mass, the content of the organic filler is preferably 0.1% to 20% by mass, and more preferably 0.2% to 10% by mass. %, More preferably 0.3 to 5 mass% or 0.5 to 3 mass%.

-(H) Any Additive- (1) In one embodiment, the resin composition may further include other additives if necessary. Examples of the other additives include organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds. And resin additives such as tackifiers, defoamers, leveling agents, adhesion-imparting agents, and coloring agents.

<Physical properties and uses of the resin composition layer> The transmission coefficient P of the cured product obtained by thermally curing the resin composition layer at 100 ° C for 30 minutes and further at 180 ° C for 30 minutes is easily changed from the balance of the physical properties of the resin composition. Good, from the viewpoint of improving substrate adhesion, it is 1.2cc / m ² · mm ^-1 · day · atom or more, preferably 1.5cc / m ² · mm ^-1 · day · atom or more, more preferably 2cc / m ²・ mm ^-1・ day ・ atom or more. The upper limit of this transmission coefficient P makes it difficult for oxygen to pass through the insulating layer. As a result, from the viewpoint of suppressing oxidation of metals such as copper foil, which is the base of the insulating layer, and improving the adhesion of the base, it is 5cc / m ² · mm ^-1 · day · atom or less, preferably 4.5cc / m ² · mm ^-1 · day · atom or less, and more preferably 4cc / m ² · mm ^-1 · day · atom or less. The transmission coefficient P can be within this range by adjusting the content of a hardener, an inorganic filler, a thermoplastic resin, and the like. The transmission coefficient P can be measured as described in "Measurement of oxygen transmission rate and transmission coefficient" described later.

When the resin composition layer is thermally cured at 100 ° C. for 30 minutes, and further cured at 180 ° C. for 30 minutes, the oxygen permeability of the cured product is measured, and the thickness of the cured product is measured as 60 μm. The balance of the physical properties of the resin composition is likely to change. Good, from the viewpoint of improving the adhesion of the substrate, it is preferably 20cc / m ² · day · atom or more, more preferably 25cc / m ² · day · atom or more, and even more preferably 30cc / m ² · day・ Atom or more. The upper limit of the oxygen transmission rate makes it difficult for oxygen to pass through the insulating layer. As a result, from the viewpoint of suppressing the oxidation of metals such as copper foil, which is the base of the insulating layer, and improving the adhesion of the base, it is preferably 80cc / m ² · Below day ・ atom, more preferably 75cc / m ²・ day ・ atom or less, and even more preferably 70cc / m ²・ day ・ atom or less. The oxygen transmission rate can be measured as described in "Measurement of oxygen transmission rate and transmission coefficient" described later.

The cured product obtained by thermally curing the resin composition layer at 100 ° C for 30 minutes and further at 180 ° C for 30 minutes has a transmission coefficient P of 1.2cc / m ² · mm ^-1 · day · atom 5cc / m ² or more · Below mm ^-1 · day · atom, it exhibits excellent peel strength (copper adhesion) with copper foil. That is, an insulating layer having excellent substrate adhesion is provided. As the substrate adhesion, the load required for peeling a small piece with a width of 10 mm is preferably 0.2 kgf or more, more preferably 0.25 kgf or more, and still more preferably 0.3 kgf or more. The upper limit is preferably 1 kgf or less, 10 kgf or less. The adhesion of the substrate can be measured as described in "Measurement of the adhesion of the substrate" described later.

The cured product obtained by thermally curing the resin composition layer at 100 ° C. for 30 minutes and further at 180 ° C. for 30 minutes exhibits excellent characteristics of reflow resistance. That is, an insulating layer having excellent reflow resistance is provided. Even if the insulating layer formed using the resin composition layer is subjected to a reflow step of reproducing the reflow temperature at a peak temperature of 260 ° C more than 20 times, the peeling between the insulating layer and the conductor layer is preferably 2 or less, more preferably, there is no insulating layer. Delamination from the conductor layer. The reflow resistance can be evaluated by a method described in "Evaluation of Reflow Resistance" described later.

Even if the thickness of the resin composition layer of the present invention is as thin as 15 μm or less, it can bring an insulating layer (hardened product of the resin composition layer) having excellent substrate adhesion and reflow resistance. Accordingly, the resin composition layer of the present invention can be suitably used as a resin composition for forming an insulating layer included in an electronic part. For example, the resin composition layer can be suitably used for forming wiring by a semi-additive method (a method using the semi-additive method). Used for wiring formation) resin composition. The resin composition layer can be suitably used as a resin composition layer for forming an insulating layer of a printed circuit board (for forming an insulating layer of a printed circuit board), and can be more suitable as an interlayer insulation for forming a printed circuit board. A resin composition layer (a resin composition layer for an interlayer insulating layer of a printed wiring board) is used.

The resin composition of the present invention can also be suitably used as a resin composition for forming a conductor layer (a resin composition for forming an insulating layer for forming a conductor layer). Furthermore, a resin composition for sealing electronic components can be suitably used, for example, it can also be suitably used as a resin composition for sealing a semiconductor wafer (resin composition for forming a sealing layer of a semiconductor wafer).

[Resin sheet] The resin sheet of the present invention includes a support and a resin composition layer of the present invention provided on the support. The resin composition layer is as described in [Resin composition layer].

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

When a film made of a plastic material is used as a support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes referred to as "PET"), polyethylene naphthalate (hereinafter referred to as "PET") (Hereinafter referred to as "PEN"), polyester, polycarbonate (hereinafter sometimes referred to as "PC"), acrylic acid such as polymethylmethacrylate (PMMA), cyclic polyolefin, and triethylfluorene-based fiber (TAC), polyether sulfide (PES), polyetherketone, polyimide and the like. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and cheap polyethylene terephthalate is particularly preferred.

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

The support may be subjected to a matting treatment, a corona treatment, or an antistatic treatment on the surface bonded to the resin composition layer.

Moreover, as a support body, the support body with a mold release layer which has a mold release layer can be used for the surface joined to a resin composition layer. Examples of the release agent used in the release layer of a support with a release layer include a resin selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. 1 or more release agents. Commercially available products can be used as the support with a release layer. Examples of the PET film having a release layer containing an alkyd resin-based release agent as a main component are "SK-1" and "AL" manufactured by Lindec Corporation. -5 "," AL-7 "," Lumirror T60 "made by Toray," Purex "made by Teijin," Unipiel "made by Unitika, etc.

The thickness of the support is not particularly limited, but it is preferably in the range of 5 to 75 μm, and more preferably in the range of 10 to 60 μm. When a support with a release layer is used, the thickness of the entire support with a release layer is preferably in the above range.

In one embodiment, the resin sheet may further include other layers if necessary. Examples of the other layer include a surface provided on a surface of the resin composition layer that is not bonded to the support (that is, a surface opposite to the support), a protective film based on the support, and the like. Although the thickness of the protective film is not particularly limited, it is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to suppress adhesion or scratches on the surface of the resin composition layer from dirt and the like.

The resin sheet can be produced, for example, by preparing a resin varnish dissolved in an organic solvent to dissolve the resin composition, applying the resin varnish to a support using a die coater or the like, and drying the resin varnish to form a resin composition layer.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK), cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and Acetates such as carbitol acetate, cellulosics and carbitol such as butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylethyl Amidamine-based solvents such as fluorenamine (DMAc) and N-methylpyrrolidone. The organic solvents may be used singly or in combination of two or more kinds.

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

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

[Printed Circuit Board] The printed circuit board of the present invention includes a first conductor layer, a second conductor layer, and an insulating layer. The insulating layer contains a resin composition containing (A) an epoxy resin and (B) a hardener, and has a thickness of 15 μm or less, and a heat transfer coefficient of a hardened product obtained by heat curing at 100 ° C. for 30 minutes and further at 180 ° C. for 30 minutes P is a cured product of a resin composition layer of 1.2 cc / m ² · mm ^-1 · day · atom or more and 5 cc / m ² · mm ^-1 · day · atom or less. The insulating layer is provided between the first conductor layer and the second conductor layer, and insulates the first conductor layer and the second conductor layer (the conductor layer is sometimes referred to as a wiring layer). As a suitable embodiment, the insulating layer is formed of a cured product of the resin composition layer of the resin sheet of the present invention.

The thickness of the insulating layer between the first and second conductor layers is preferably 6 μm or less, more preferably 5.5 μm or less, and even more preferably 5 μm or less. Although the lower limit is not particularly limited, it 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 an example shown in FIG. 1, and the main surface 11 of the first conductor layer 1 and the second conductor layer The thickness t1 of the insulating layer 3 between the main surfaces 21 of 2. The first and second conductor layers are conductor layers adjacent to each other through the insulating layer, and the main surface 11 and the main surface 21 face each other.

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

A printed circuit board can be manufactured by using the above-mentioned resin sheet and including the following steps (I) and (II). (I) a step of laminating the resin composition layer of the resin sheet and the inner layer substrate on the inner substrate (II) a step of forming an insulating layer of the thermosetting resin composition layer

The "inner substrate" used in step (I) refers to a member that becomes a substrate of a printed circuit board. Examples include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermal substrates. Hardened polyphenylene ether substrate, etc. In addition, the substrate may have a conductor layer on one or both sides, and the conductor layer may be patterned. An inner layer substrate on which one or both sides of the substrate form a conductor layer (circuit) is sometimes referred to as an "inner layer circuit substrate." In addition, when manufacturing a printed circuit board, an intermediate manufactured product that further forms an insulating layer and / or a conductor layer is also included in the so-called "inner substrate" of the present invention. When the printed circuit board is a part-embedded circuit board, the inner substrate of the built-in part can be used.

Lamination of the inner substrate and the resin sheet can be performed, for example, by heat-pressing the resin sheet from the support side to the inner substrate. Examples of a member (hereinafter, also referred to as a "heat-compression-bonding member") for heat-pressing a resin sheet on an inner substrate include a heated metal plate (SUS mirror plate, etc.), a metal roller (SUS roller), and the like. Still, it is preferable not to press the thermocompression-bonding member directly on the resin sheet, but to press the unevenness on the surface of the inner-layer substrate so that the resin sheet fully follows, and press it through an elastic material such as heat-resistant rubber.

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

Lamination can be performed by a commercially available vacuum laminator. Examples of commercially available vacuum laminators include vacuum pressure laminators made by Meiki Seisakusho, vacuum applicators made by Nikko Materials Co., Ltd., and batch vacuum pressure laminators.

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

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

In step (II), the thermosetting resin composition layer forms an insulating layer.

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

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

Before the resin composition layer is thermally cured, the resin composition layer may be pre-heated at a temperature lower than the curing temperature. For example, before the thermosetting resin composition layer, the resin composition layer may be preheated at a temperature of 50 ° C to 120 ° C (preferably 60 ° C to 115 ° C, more preferably 70 ° C to 110 ° C). More than minutes (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, even more preferably 15 minutes to 100 minutes).

When manufacturing a printed circuit board, (III) a step of drilling an insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductive layer may be further performed. These steps (III) to (V) can be carried out by various methods known to those having ordinary knowledge in the field of the present invention used in the manufacture of printed circuit boards. Moreover, when the support is removed after step (II), the support may be removed between step (II) and step (III), between step (III) and step (IV), or step (IV). And step (V). In addition, if necessary, the formation of the insulating layer and the conductor layer in steps (II) to (V) can be repeatedly performed to form a multilayer wiring board. In this case, it is preferable that the thickness of the insulating layer between the individual conductor layers (t1 in FIG. 1) is within the above range.

Step (III) is a step of drilling holes in the insulating layer, thereby forming holes such as through holes, through holes, and the like in the insulating layer. Step (III) can be performed using, for example, a drill, a laser, a plasma, or the like according to the composition of the resin composition used for forming the insulating layer. The size or shape of the hole can be appropriately determined according to the design of the printed circuit board.

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

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

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

The conductive material used for the conductive layer is not particularly limited. In a suitable embodiment, the conductor layer includes one selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. Above the metal. The conductor layer may be a single metal layer or an alloy layer. Examples of the alloy layer include an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy). ). Among them, from the viewpoints of versatility of forming the conductor layer, cost, and ease of patterning, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or nickel is preferred.・ An 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 and chromium alloy, Even more preferred is a single metal layer of copper.

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

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

In one embodiment, the conductive layer can be formed by plating. For example, a conventionally known technique such as a semi-additive method and a full-additive method can be used to plate the surface of an insulating layer to form a conductive layer having a desired wiring pattern. From the viewpoint of simplicity of manufacturing, it is preferably Formed by semi-additive method. Hereinafter, an example in which a conductor layer is formed by a semi-additive method is shown.

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

The resin sheet of the present invention can be suitably used when the printed circuit board is a built-in circuit board because the insulating layer also has a good part embedding property. The component-embedded circuit board can be manufactured by a well-known manufacturing method.

The printed circuit board manufactured using the resin sheet of the present invention can be in the form of an insulating layer that is a cured product of the resin composition layer of the resin sheet and an embedded wiring layer embedded in the insulating layer.

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

Examples of the semiconductor device include various semiconductor devices used in electrical products (such as computers, mobile phones, digital cameras, and televisions) and vehicles (such as motorcycles, automobiles, trains, ships, and aircraft).

The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor wafer) due to a conductive portion of a printed circuit board. The so-called "conducting place" means "a place where the electric signal is transmitted on the printed circuit board". The place may be a surface or an embedded place. The semiconductor wafer is not particularly limited as long as it is an electric circuit element using a semiconductor as a material.

The method of mounting a semiconductor wafer when manufacturing a semiconductor device is not particularly limited as long as the semiconductor wafer functions effectively. Specific examples include a wire bonding mounting method, a flip chip mounting method, and a bump-free method. A method for mounting a stacked layer (BBUL), a method for mounting an anisotropic conductive film (ACF), a method for mounting a non-conductive film (NCF), and the like. Here, the so-called "mounting method by a bumpless layer (BBUL)" is a "mounting method of directly embedding a semiconductor wafer into a recessed portion of a printed circuit board and connecting the semiconductor wafer to the wiring on the printed circuit board." [Example]

Hereinafter, the present invention will be specifically described by way of examples. The invention is not limited to these examples. In the following, the "parts" and "%" of the quantities, unless otherwise specified, mean "parts by mass" and "% by mass", respectively.

<Measurement of the average particle diameter of the inorganic filler> (1) Weigh 100 mg of the inorganic filler, 0.1 g of a dispersant ("SN9228" manufactured by Sannopco), and 10 g of methyl ethyl ketone in a vial, and disperse it in ultrasonic waves for 20 minutes. A laser diffraction type particle size distribution measuring device ("SALD-2200" manufactured by Shimadzu Corporation) was used to measure the particle size distribution in a batch cell method to calculate the average particle diameter by the median diameter.

<Measurement of Specific Surface Area of Inorganic Filling Materials> The BET automatic specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) was used to adsorb nitrogen on the sample surface, and the specific surface area was calculated using the BET multi-point method to measure the inorganic filling materials. Of specific surface area.

<Inorganic filler used> Inorganic filler 1: 100 parts with respect to spherical silica ("UFP-30" manufactured by Denki Kogyo Co., Ltd., with an average particle diameter of 0.078 μm and a specific surface area of 30.7 m ² / g). N-phenyl-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Industry Co., Ltd., KBM573) 2 parts surface treatment. Inorganic filler 2: 100 parts of spherical silica ("SC2500SQ" manufactured by Admatex, average particle size 0.77 μm, specific surface area 11.2 m ² / g), N-phenyl-3-aminopropyltrimethoxy 1 part of a surface treatment based on silane (manufactured by Shin-Etsu Chemical Industry Co., Ltd., KBM573).

<Preparation of Resin Composition 1> 6 parts of Bisphenol-type xylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent approximately 185), naphthalene type epoxy resin (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) "ESN475V", 5 parts epoxy equivalent 332), 15 parts bisphenol AF epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 238), cyclohexane epoxy resin (Mitsubishi Chemical 2 parts of "ZX1658GS" manufactured by the company, epoxy equivalent weight of about 135), phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, 30% by mass of cyclohexanone: methyl ethyl ketone (MEK): 1: (1 solution, Mw = 35000) 2 parts, stirred in a mixed solvent of 20 parts of solvent naphtha and 10 parts of cyclohexanone, and dissolved by heating. After cooling to room temperature, a cresol novolac-based hardener containing a triazine skeleton ("LA-3018-50P" manufactured by DIC Corporation), a hydroxyl equivalent of about 151, and 2-methoxypropanol at a solid content of 50% were mixed thereto. Solution) 4 parts, active ester-based hardener ("EXB-8150-65T" manufactured by DIC Corporation, approximately 229 active group equivalent, toluene solution with 65% by mass of non-volatile content) 6 parts, inorganic filler 150 parts, amine-based 0.05 parts of a hardening accelerator (4-dimethylaminopyridine (DMAP)) was uniformly dispersed in a high-speed rotary mixer, and then filtered through a filter cartridge ("SHP020" manufactured by ROKITECHNO) to prepare a resin composition 1.

<Preparation of Resin Composition 2> 6 parts of Biben cresol-type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185), naphthalene-type epoxy resin (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) "ESN475V", 5 parts epoxy equivalent, about 332), 15 parts bisphenol AF type epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent about 238), bisphenol type epoxy resin (Nippon Steel) "ZX1059" manufactured by Sumikin Chemical Co., Ltd., epoxy equivalent equivalent of about 169, 4 parts of bisphenol A type and bisphenol F type 1: 1 mixed product, naphthyl ether type epoxy resin ("EXA-7311 manufactured by DIC Corporation" -G4 ", 2 parts epoxy equivalent, about 213, phenoxy resin (" YL7500BH30 "manufactured by Mitsubishi Chemical Corporation), 30% by mass solid solution of cyclohexanone: methyl ethyl ketone (MEK) in a 1: 1 solution (Mw = 44000) 2 parts, mixed in a solvent mixture of 20 parts of solvent naphtha and 10 parts of cyclohexanone while stirring to make it heat-dissolve. After cooling to room temperature, a cresol novolac-based hardener containing a triazine skeleton ("LA-3018-50P" manufactured by DIC Corporation), a hydroxyl equivalent of about 151, and 2-methoxypropanol at a solid content of 50% were mixed thereto. Solution) 4 parts, active ester-based hardener ("EXB-8000L-65M" manufactured by DIC Corporation, active group equivalent of about 220, non-volatile content 65% by mass MEK solution) 6 parts, inorganic filler 1 40 parts, amine-based 0.05 parts of a hardening accelerator (4-dimethylaminopyridine (DMAP)) was uniformly dispersed in a high-speed rotary mixer, and then filtered through a filter cartridge ("SHP020" manufactured by ROKITECHNO) to prepare a resin composition 2.

<Preparation of Resin Composition 3> 6 parts of Biben cresol-type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185), naphthalene-type epoxy resin (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) "ESN475V", 5 parts epoxy equivalent, about 332), 15 parts bisphenol AF type epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent about 238), bisphenol type epoxy resin (Nippon Steel) "ZX1059" manufactured by Sumikin Chemical Co., Ltd., epoxy equivalent equivalent of about 169, 4 parts of bisphenol A type and bisphenol F type 1: 1 mixed product, naphthyl ether type epoxy resin ("EXA-7311 manufactured by DIC Corporation" -G4 ", 2 parts epoxy equivalent, about 213, phenoxy resin (" YL7500BH30 "manufactured by Mitsubishi Chemical Corporation), 30% by mass solid solution of cyclohexanone: methyl ethyl ketone (MEK) in a 1: 1 solution (Mw = 44000) 2 parts, mixed in a solvent mixture of 20 parts of solvent naphtha and 10 parts of cyclohexanone while stirring to make it heat-dissolve. After cooling to room temperature, a cresol novolac-based hardener containing a triazine skeleton ("LA-3018-50P" manufactured by DIC Corporation), a hydroxyl equivalent of about 151, and 2-methoxypropanol at a solid content of 50% were mixed thereto. Solution) 4 parts, active ester-based hardener ("EXB-8000L-65M" manufactured by DIC Corporation, active group equivalent of about 220, MEK solution with 65% by mass of non-volatile content), 1 40 parts of inorganic filler, amine-based 0.05 parts of a hardening accelerator (4-dimethylaminopyridine (DMAP)) was uniformly dispersed in a high-speed rotary mixer, and then filtered through a filter cartridge ("SHP020" manufactured by ROKITECHNO) to prepare a resin composition 3.

<Preparation of Resin Composition 4> 6 parts of Bibian xylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185), naphthalene type epoxy resin (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) "ESN475V", 5 parts epoxy equivalent 332), 15 parts bisphenol AF epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 238), cyclohexane epoxy resin (Mitsubishi Chemical 2 parts of "ZX1658GS" manufactured by the company, epoxy equivalent weight of about 135), phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, 30% by mass of cyclohexanone: methyl ethyl ketone (MEK): 1: 1 solution) 2 parts, and mixed by heating in a mixed solvent of 20 parts of solvent naphtha and 10 parts of cyclohexanone to heat and dissolve. After cooling to room temperature, a cresol novolac-based hardener containing a triazine skeleton ("LA-3018-50P" manufactured by DIC Corporation), a hydroxyl equivalent of about 151, and 2-methoxypropanol at a solid content of 50% were mixed thereto. Solution) 4 parts, active ester-based hardener ("EXB-8000L-65M" manufactured by DIC Corporation, active group equivalent of about 220, MEK solution with 65% by mass of non-volatile content), 2 160 parts of inorganic filler, amine-based 0.05 parts of a hardening accelerator (4-dimethylaminopyridine (DMAP)) was uniformly dispersed in a high-speed rotary mixer, and then filtered through a filter cartridge ("SHP020" manufactured by ROKITECHNO) to prepare a resin composition 4.

The components used for the preparation of the resin compositions 1 to 4 and their blending amounts (parts by mass of nonvolatile matter) are shown in the following table. The abbreviations and the like in the following tables are as follows. Content of hardener: content of the hardener when the resin component is set to 100% by mass in the resin composition Active ester-based hardener content: active ester when the resin component is set to 100% by mass in the resin composition Content of hardener Content of inorganic filler: Content of inorganic filler when the non-volatile content in the resin composition is set to 100% by mass

<Production of Resin Sheets> As a support, a PET film ("Lumirror R80" manufactured by Toray Co., Ltd.) with a mold release treatment ("AL-5" manufactured by Lindec Corporation) is prepared. Softening point: 130 ° C, "Release PET").

Each resin composition was coated on a release PET so that the thickness of the dried resin composition layer became 10 μm, and then uniformly coated on a mold coater, and dried at 70 ° C. to 95 ° C. for 2 minutes, and then released from the mold. A resin composition layer was obtained on PET. Next, a rough surface of a polypropylene film ("Alfan MA-411" manufactured by Oji Ftex Co., Ltd., thickness 15 µm) was bonded to the resin composition layer as a protective film on the surface not bonded to the support of the resin sheet. Laminate. Thereby, the resin sheet A which consists of the order of a release PET (support body), a resin composition layer, and a protective film was obtained. The resin sheet B was obtained in the same manner as the resin sheet A except that each resin composition was uniformly applied to a die coater so that the thickness of the dried resin composition layer became 30 μm.

<Measurement of thickness of resin composition layer and the like> ＞ The thickness is measured using a contact film thickness meter (manufactured by Mitutoyo Corporation, MCD-25MJ).

<Evaluation of reflow resistance>-Production of evaluation substrate A- (1) Copper-clad laminates are copper-clad laminates, which are prepared on both sides of a glass cloth substrate with epoxy resin on both sides and copper-clad laminates ( The thickness of the copper foil is 3 μm, the thickness of the substrate is 0.15 mm, and “HL832NSF LCA” manufactured by Mitsubishi Gas Chemical Co., Ltd. (255 × 340 mm size).

(2) Lamination of resin sheets The protective films were peeled from each resin sheet A produced in the examples and comparative examples, and a batch vacuum pressure laminator (manufactured by Nikko Material Co., Ltd., 2-stage stacking laminator, CVP700) was used. The resin composition layer and the copper-clad laminate are bonded together, and laminated on both sides of the copper-clad laminate. The lamination system was carried out by depressurizing for 30 seconds to reduce the air pressure to 13 hPa or less, and performing pressure bonding at 130 ° C and a pressure of 0.74 MPa for 45 seconds. Next, hot stamping was performed at 120 ° C. and a pressure of 0.5 MPa for 75 seconds.

(3) Thermal hardening of the resin composition layer The copper-clad laminate of the laminated resin sheet was put into an oven at 100 ° C for 30 minutes, and then transferred to an oven at 180 ° C for 30 minutes to form an insulating layer. Mold PET. This is referred to as a cured substrate A.

(4) Step for roughening treatment (1) The insulation layer of the hardened substrate A is subjected to a slag removing treatment as a roughening treatment. As the desmearing treatment, the following wet desmearing treatment was performed.

Wet deslagging treatment: immerse in a swelling solution ("Swelling dip · Securigant P" manufactured by Atotech Japan, an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60 ° C for 10 minutes, and then immerse in an oxidant solution ( "Concentrate Compact CP" manufactured by Atotech Japan, an aqueous solution with a potassium permanganate concentration of about 6% and a sodium hydroxide concentration of about 4%, was immersed at 80 ° C for 20 minutes, and finally neutralized with a solution ("Reduction solution" manufactured by Atotech Japan)・ Securigant P ", sulfuric acid aqueous solution) was immersed at 40 ° C for 5 minutes, and then dried at 80 ° C for 15 minutes. This was designated as roughened substrate A.

(5) Step of forming conductor layer (5-1) Electroless plating step Since a conductor layer is formed on the surface of the insulating layer of roughened substrate A, a plating step including the following steps 1 to 6 is performed (using Atotech Japan) Copper plating step of the prepared chemical solution) to form a conductor layer.

1. Alkali cleaning (cleaning and charge adjustment of the surface of the insulating layer provided with through holes) The surface of the roughened substrate A was cleaned with Cleaning Cleaner Securiganth 902 (trade name) for 5 minutes at 60 ° C. 2. Soft etching (cleaning in the through hole) The surface of the roughened substrate A is treated with a sulfuric acid acid sodium peroxodisulfate aqueous solution at 30 ° C for 1 minute. 3. Pre-dip (adjustment of charge on the surface of the insulating layer imparted to Pd) Pre The surface of the roughened substrate A was treated with Pre. Dip Neoganth B (trade name) at room temperature for 1 minute. 4. Accelerator application (application of Pd to the surface of the insulating layer) Activ The surface of the roughened substrate A was treated with Activator Neoganth 834 (trade name) for 5 minutes at 35 ° C. 5. Reduction (reduction of Pd imparted by the insulating layer) The surface of the roughened substrate A was treated with a mixture of Reducer Neoganth WA (trade name) and Reducer Acceralator 810 mod. (Trade name) at 30 ° C for 5 minutes. 6. Electroless copper plating step (Cu is deposited on the surface of the insulating layer (Pd surface)) The surface of the roughened substrate A is Basic Solution Printganth MSK-DK (trade name), Copper Solution Printganth MSK (trade name), The mixed solution with Stabilizer Printganth MSK-DK (trade name) and Reducer Cu (trade name) was treated at 35 ° C for 15 minutes. The thickness of the formed electroless copper-plated layer was 1 μm.

After the electroless copper plating step, electrolytic copper plating is performed to form an electrolytic copper plating layer (conductor layer) with a thickness of 14 μm (the total thickness with the electroless copper plating layer is about 15 μm). This was designated as evaluation substrate A.

-Evaluation of reflow resistance--The evaluation substrate A was cut into a test piece of 100 mm × 100 mm. The obtained test piece was described in IPC / JEDEC J-STD-020C ("Moisture / Reflow Sensitivity Classification For Nonhermetic Solid State Surface Mount Devices", July 2004) using a reflow device ("HAS6116" manufactured by Anton). Reflow temperature file (lead-free assembly file; peak temperature 260 ° C), repeat the simulated reflow step 20 times. Furthermore, the reflow resistance was evaluated according to the following evaluation criteria. Evaluation criteria: ○: The peeling between the insulating layer and the conductor layer is 2 or less ×: The peeling between the insulating layer and the conductor layer is 3 or more

<Measurement of substrate adhesion> (1) Substrate treatment of copper foil The glossy surface of "3EC-III" (electrical copper foil, 35 μm) manufactured by Mitsui Metal Mining Corporation was dipped in Mec etch bond "CZ-8101" manufactured by Mec Corporation Roughening treatment (Ra value = 1 μm) was performed on the copper surface, and rust prevention treatment (CL8300) was performed. This copper foil is called a CZ copper foil. Furthermore, it heat-processed in the oven at 130 degreeC for 30 minutes.

(2) Lamination of copper foil and formation of an insulating layer A protective film was peeled from each resin sheet A produced in the examples and comparative examples, and a batch type vacuum pressure laminator ("MVLP-500" manufactured by Meiki Co., Ltd.) was used. The two sides of the inner-layer circuit board are laminated so that the resin composition layer is bonded to the inner-layer circuit board. The lamination treatment was performed by depressurizing for 30 seconds to reduce the air pressure to 13 hPa or less, and performing pressure bonding at 100 ° C and a pressure of 0.74 MPa for 30 seconds. After lamination, the release PET of the support was peeled. The treated surface of the CZ copper foil of "3EC-III" was laminated on the resin composition layer of the release support under the same conditions as described above. Then, the resin composition layer was cured under a curing condition of 190 ° C and 90 minutes to form an insulating layer, and a sample was produced.

(3) Measurement of copper foil peeling strength (base adhesion) 基底 Cut the produced sample into small pieces of 150 × 30 mm. Using a cutter on the small piece of copper foil, insert a slice of 10 mm wide and 100 mm in length, and peel off one end of the copper foil. Using an Instron universal testing machine, the load when peeling 35 mm in a vertical direction at a speed of 50 mm / min at room temperature was measured in accordance with JIS C6481 and evaluated using the following criteria. Evaluation criteria ○: The measurement result of the substrate adhesion is 0.2 kgf or more ×: The measurement result of the substrate adhesion is less than 0.2 kgf

<Measurement of oxygen transmission rate and transmission coefficient> -Production of hardened sheet- 硬化 Remove the protective film from each resin sheet B produced in the examples and comparative examples, and use a batch type vacuum pressure laminator (manufactured by Nikko Material Co., 2 steps) Stack laminator, CVP700), and two resin sheets B were laminated so that the resin composition layers were bonded together. The lamination system was carried out by depressurizing for 30 seconds to reduce the air pressure to 13 hPa or less, and performing pressure bonding at 130 ° C and a pressure of 0.74 MPa for 45 seconds. Then, the release PET on one side was peeled off, and the resin composition layer was cured under a curing condition of 90 ° C. for 90 minutes, and then the release PET on the other side was peeled off to produce a cured sheet B.

-Measurement of oxygen transmission rate and transmission coefficient- Using an oxygen transmission rate measuring device (manufactured by MOCON, OX-TRAN2 / 21), in accordance with JIS-K7126 (isobaric method), at 23 ° C, 0% RH and 23 The oxygen transmission rate of the cured sheet B was measured under an environment of ℃ and 90% RH. In addition, the RH system means relative humidity. The transmission coefficient P (oxygen transmission coefficient P) was calculated by taking the oxygen transmission rate of the cured sheet B as a reference and removing the thickness. The case where the transmission coefficient P is 5.0 cc / m ² · mm ^-1 · day · atom or less is evaluated as "○", and the case where the transmission coefficient P exceeds 5.0 cc / m ² · mm ^-1 · day · atom is evaluated as "○" × ". Also, a case where the transmission coefficient P is 1.2 cc / m ² · mm ^-1 · day · atom or more is evaluated as "○", and a case where the transmission coefficient P is less than 1.2 cc / m ² · mm ^-1 · day · atom is evaluated. Evaluation was "×".

In Examples 1 to 2, it was confirmed that even when the components (C) to (E) were not contained, the results were the same as those of the above examples, although the degree was poor.

1‧‧‧ the first conductor layer

11‧‧‧ the main surface of the first conductor layer

2‧‧‧ 2nd conductor layer

21‧‧‧ the main surface of the second conductor layer

3‧‧‧ Insulation

t1‧‧‧The distance between the first conductor layer and the second conductor layer (thickness of the insulating layer between the first and second conductor layers)

t2‧‧‧Thickness of the entire insulation layer

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

Claims (16)

A resin composition layer is a resin composition layer containing a resin composition containing (A) an epoxy resin and (B) a hardener, and is characterized in that the thickness of the resin composition layer is 15 μm or less, and the resin composition layer is The transmittance P of the hardened material obtained by thermally curing at 100 ° C for 30 minutes and further at 180 ° C for 30 minutes is 1.2cc / m ² · mm ^-1 · day · atom 5cc / m ² · mm ^-1 · day or more below atom. For example, the resin composition layer of claim 1 is used for wiring formation by a semi-additive method. The resin composition layer according to claim 1, which contains (C) an inorganic filler. The resin composition layer of claim 3, wherein when the non-volatile content in the resin composition is 100% by mass, the content of the component (C) is 40% by mass or more and 80% by mass or less. The resin composition layer according to claim 3, wherein the average particle diameter of the component (C) is 0.05 μm or more and 0.35 μm or less. The resin composition layer according to claim 1, wherein when the resin component is set to 100% by mass, the content of the (B) component is 20% by mass or less. The resin composition layer according to claim 1, wherein the component (B) contains an active ester-based hardener. The resin composition layer according to claim 7, wherein when the resin component is set to 100% by mass, the content of the active ester-based hardener is 15% by mass or less. The resin composition layer according to claim 1, which contains (D) a thermoplastic resin. The resin composition layer according to claim 9, wherein the weight average molecular weight of the component (D) is 38,000 or more. For example, the resin composition layer of claim 1, wherein the transmission coefficient P is 2cc / m ² · mm ^-1 · day · atom or more and 4cc / m ² · mm ^-1 · day · atom or less. The resin composition layer of claim 1 is for forming an insulating layer of a printed circuit board. For example, the resin composition layer of claim 1 is for forming an interlayer insulating layer of a printed circuit board. A resin sheet comprising a support and a resin composition layer according to any one of claims 1 to 13 provided on the support. A printed circuit board is a printed circuit board comprising a first conductor layer, a second conductor layer, and an insulation layer formed between the first conductor layer and the second conductor layer, characterized in that the insulation layer is as in claim 1 The hardened | cured material of the resin composition layer in any one of -13. A semiconductor device comprising a printed circuit board as claimed in claim 15.