TWI820018B - resin composition layer - Google Patents

Abstract

An object of the present invention is to provide a resin composition layer and the like that can obtain a cured product having excellent substrate adhesion and reflow resistance even if the thickness is thin. The solution of the present invention is a resin composition layer, which is a resin composition layer containing a resin composition containing (A) epoxy resin and (B) hardener, and is characterized in that the thickness of the resin composition layer is 15 μm or less. The transmission coefficient P of the cured product obtained by thermally curing the resin composition layer at 100°C for 30 minutes and then at 180°C for 30 minutes is 1.2cc/m ²・mm ^-1・day・atom or more 5cc/m ²・mm ^-1・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 equipment, printed circuit boards have been further thinned, and along with this, wiring circuits in inner substrates have been miniaturized. For example, Patent Document 1 describes a resin sheet (adhesive film) that includes a support and a resin composition layer and can be used for fine wiring. [Prior art documents] [Patent documents]

[Patent Document 1] Japanese Patent Application Publication No. 2014-36051

[Problem to be solved by the invention]

In order to achieve further miniaturization and thinning of electronic equipment, the inventors studied thinning the resin composition layer of the resin sheet. However, they found that when the thin resin composition layer is suitable for build-up applications, it is subject to the limitations of semiconductor wafers. Due to the influence of the high-temperature environment during installation, the adhesion may not be fully ensured.

The object of the present invention is to provide a resin composition layer that can obtain a cured product with excellent substrate adhesion and reflow resistance even if the thickness is thin; a resin sheet including the resin composition layer; and a resin composition layer formed using the resin composition layer. The insulating layer of printed circuit boards and semiconductor devices. [Means used to solve problems]

In order to achieve the object of the present invention, the present inventors have conducted diligent research and found that when the thickness of the resin composition layer is thin, oxygen in the cured material of the resin composition layer easily penetrates, resulting in deterioration of adhesion. Therefore, by adjusting the transmission coefficient P of the cured material of the resin composition layer so that it falls within a specified range, it was found that even if the thickness of the resin composition layer is thinned, excellent substrate adhesion and reflow resistance can be obtained. The cured product of the resin composition layer finally completes the present invention.

That is, the present invention includes the following contents. [1] A resin composition layer including a resin composition containing (A) epoxy resin and (B) hardener, characterized in that the thickness of the resin composition layer is 15 μm or less, and the resin is The composition layer is thermally cured at 100°C for 30 minutes, and further thermally cured at 180°C for 30 minutes. The transmission coefficient P of the cured product is 1.2cc/m ²・mm ^-1・day・atom or more 5cc/m ²・mm ^-1・day・atom or less. [2] The resin composition layer as described in [1], which is used for wiring formation by a semi-additive process. [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 the content of component (C) is 40 mass% or more and 80 mass% or less when the non-volatile components in the resin composition are 100 mass%. [5] The resin composition layer according to [3] or [4], wherein the average particle diameter of 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 the content of component (B) is 20 mass% or less when the resin component is 100 mass%. [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 the content of the active ester-based hardener is 15 mass% or less when the resin component is 100 mass%. [9] The resin composition layer according to any one of [1] to [8], which contains (D) thermoplastic resin. [10] The resin composition layer according to [9], wherein the weight average molecular weight of 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 and 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 to form an insulating layer of a printed circuit board. [13] The resin composition layer according to any one of [1] to [12], which is used to form an interlayer insulating layer of a printed circuit board. [14] A resin sheet including a support and a resin composition layer according to any one of [1] to [13] provided on the support. [15] A printed circuit board, which is a printed circuit board including a first conductor layer, a second conductor layer and an insulating layer formed between the first conductor layer and the second conductor layer, characterized in that the insulating layer is as follows A cured product of the resin composition layer according to any one of [1] to [13]. [16] A semiconductor device including the printed circuit board described in [15]. [Effects of the invention]

According to the present invention, it is possible to provide a resin composition layer that can obtain a cured product with excellent substrate adhesion and reflow resistance even if the thickness is thin; a resin sheet including the resin composition layer; and a resin composition layer that has the advantages of using the resin composition layer. The insulating layer formed on printed circuit boards and semiconductor devices.

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

The "resin component" refers to the component excluding (C) the inorganic filler mentioned below 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 including a resin composition containing (A) epoxy resin and (B) hardener, and is characterized in that the thickness of the resin composition layer is 15 μm or less. The transmission coefficient P of the cured product obtained by thermally curing the resin composition layer at 100°C for 30 minutes and then at 180°C for 30 minutes is 1.2cc/m ²・mm ^-1・day・atom or more 5cc/m ²・mm ^-1・day・atom or less. By adjusting the transmission coefficient P to fall within the above range, even if the thickness of the resin composition layer is 15 μm or less, it is possible to obtain a cured product that provides substrate adhesion and is excellent in reflow resistance.

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, still more preferably 8 μm or less. Although the lower limit of the thickness of the resin composition layer is not particularly limited, it may generally be 1 μm or more, 1.5 μm or more, 2 μm or more, or the like.

The resin composition layer is formed of a resin composition containing (A) epoxy resin and (B) hardener. Setting the transmission coefficient P within the above range can be achieved by adjusting each component contained in the resin composition. If necessary, the resin composition may further contain additives such as (C) inorganic fillers, (D) thermoplastic resins, (E) hardening accelerators, (F) flame retardants, and (G) organic fillers. Each component contained in the resin composition of the present invention will be described in detail below.

-(A) Epoxy resin- The resin composition contains (A) epoxy resin. Examples of the epoxy resin include dixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, bicyclo Pentylene type epoxy resin, ginseng phenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin Resin, naphthol type epoxy resin, onion type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, wire Aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro-containing epoxy resin, cyclohexane-type epoxy resin, cyclohexane Dimethanol type epoxy resin, naphthyl ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, etc. One type of epoxy resin can be used alone, or two or more types can be used in combination.

The epoxy resin is preferably an epoxy resin containing two or more epoxy groups per molecule. When the non-volatile content of the epoxy resin is defined as 100% by mass, it is preferable that at least 50% by mass or more is an epoxy resin having two or more epoxy groups per 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 "liquid epoxy resin"). "Solid epoxy resin"). The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups per molecule, and more preferably an aromatic liquid epoxy having two or more epoxy groups per molecule. resin. The solid epoxy resin is preferably a solid epoxy resin having three or more epoxy groups per molecule, and more preferably an aromatic solid epoxy resin having three or more epoxy groups per molecule. resin. In the present invention, the term "aromatic epoxy resin" means an epoxy resin having an aromatic ring in its molecule.

As the liquid epoxy resin, preferred are bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl ester type epoxy resin, Glyceryl amine type epoxy resin, phenolic novolak type epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, glycidyl amine type Epoxy resin and epoxy resin with butadiene structure, preferably bisphenol A type epoxy resin, bisphenol F type epoxy resin and cyclohexane type epoxy resin. Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC Corporation, and "828US", "jER828EL", and "825" manufactured by Mitsubishi Chemical Corporation. ", "EPIKOTE828EL" (bisphenol A type epoxy resin), "jER807", "1750" (bisphenol F type epoxy resin), "jER152" (phenol novolak type epoxy resin), "630", " 630LSD" (glycidyl amine type epoxy resin), "ZX1059" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin), manufactured by Nagase ChemteX "EX-721" (glycidyl ester type epoxy resin), "Celloxide 2021P" made by Daicel Corporation (alicyclic epoxy resin with ester skeleton), "PB-3600" (cyclic epoxy resin with butadiene structure) Oxygen resin), "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nippon Steel Chemical Corporation, "630LSD" (glycidylamine) manufactured by Mitsubishi Chemical Corporation type epoxy resin), etc. These may be used individually by 1 type, and may be used in combination of 2 or more types.

As the solid epoxy resin, preferred are dixylenol-type epoxy resin, naphthalene-type epoxy resin, naphthalene-type tetrafunctional epoxy resin, cresol novolac-type epoxy resin, and dicyclopentadiene-type epoxy resin. , ginseng phenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthyl ether type epoxy resin, onion type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type ring Oxygen resin, tetraphenylethane type epoxy resin, more preferably dixylenol type epoxy resin, naphthalene type epoxy resin, bisphenol AF type epoxy resin and naphthyl ether type epoxy resin. Specific examples of solid epoxy resins include "HP4032H" (naphthalene type epoxy resin), "HP-4700", "HP-4710" (naphthalene type tetrafunctional epoxy resin), and "N -690" (cresol novolak type epoxy resin), "N-695" (cresol novolak 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" (alkylene ether type epoxy resin ), "EPPN-502H" (ginseng phenol type epoxy resin), "NC7000L" (naphthol novolak 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 Metal Chemical Co., Ltd., “ESN485” (naphthol novolac-type epoxy resin), “YX4000H” manufactured by Mitsubishi Chemical Co., Ltd. ”, “YX4000”, “YL6121” (biphenyl-type epoxy resin), “YX4000HK” (bixylenol-type epoxy resin), “YX8800” (onion-type epoxy resin), manufactured by Osaka Gas Chemicals Co., Ltd. PG-100", "CG-500", Mitsubishi Chemical Corporation's "YL7760" (bisphenol AF type epoxy resin), "YL7800" (Fluid type epoxy resin), Mitsubishi Chemical Corporation's "jER1010" (solid bisphenol A-type epoxy resin), "jER1031S" (tetraphenylethane-type epoxy resin), etc. These may be used individually by 1 type, and may be used in combination of 2 or more types.

When a liquid epoxy resin and a solid epoxy resin are used together as component (A), the quantitative ratio (liquid epoxy resin: solid epoxy resin) of the mass ratio is preferably 1:1 to 1:20. range. By setting the ratio of liquid epoxy resin to solid epoxy resin within this range, i) moderate adhesion is obtained when used in the form of a resin sheet, ii) obtained when used in the form of a resin sheet. Sufficient flexibility, improved operability, and iii) effects such as obtaining a hardened product with sufficient breaking strength. From the viewpoint of the effects of i) to iii) above, the mass ratio of liquid epoxy resin to solid epoxy resin (liquid epoxy resin: solid epoxy resin) is more preferably 1: The range is 2 to 1:10, and more preferably the range is 1:5 to 1:10.

The content of component (A) in the resin composition is preferably 10 mass% or more when the resin component is 100 mass%, from the viewpoint of obtaining an insulating layer showing good mechanical strength and insulation reliability, and more preferably Preferably, it is 20 mass % or more, and still more preferably, it is 30 mass % or more. The upper limit of the epoxy resin content is not particularly limited as long as the effect of the present invention can be exerted, but it is preferably 60 mass% or less, more preferably 55 mass% or less, 50 mass% or less, or 45 mass% or less.

The epoxy group equivalent of component (A) is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, still more preferably 110 to 1000. By entering this range, the cross-linking density of the hardened material becomes sufficient and an insulating layer with small surface roughness can be produced. However, the epoxy group equivalent can be measured according to JIS K7236 and is the mass of the resin containing 1 equivalent of epoxy group.

The weight average molecular weight of component (A) is preferably 100 to 5,000, more preferably 250 to 3,000, still more preferably 400 to 1,500. Here, the weight average molecular weight of the epoxy resin is the weight average molecular weight in terms of polystyrene measured by the gel permeation chromatography (GPC) method.

-(B) Hardener- The resin composition contains (B) hardener. The component (B) is not particularly limited as long as it has the function of curing the component (A). Examples thereof include phenol-based curing agents, naphthol-based curing agents, active ester-based curing agents, and benzoxazine-based curing agents. Agents, cyanate ester hardeners and carbodiimide hardeners, etc. One type of hardening agent may be used alone, or two or more types may be used in combination.

As the phenol-based hardener and the naphthol-based hardener, from the viewpoint 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. Furthermore, from the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenol-based hardening agent is preferred, and a phenol-based hardening agent containing a triazine skeleton is more preferred.

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

The active ester-based hardener is not particularly limited, but generally it is preferable to use phenol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, etc. in one molecule. Compounds with two or more highly reactive ester groups. The active ester hardener is preferably obtained by the condensation reaction of a carboxylic acid compound and/or a sulfur carboxylic acid compound and a hydroxyl compound and/or a thiol compound. Especially from the viewpoint of improving heat resistance, an active ester hardener obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester type hardener obtained from a carboxylic acid compound, a phenol compound and/or a naphthol compound is more preferred. Hardener. Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and the like. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated Bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene Naphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, phlorotriol, 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 with one molecule of dicyclopentadiene.

Specifically, preferred are an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetate of phenol novolak, and a benzoyl compound containing a phenol novolak. 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 a phenylene-dicyclopentyl-phenylene group.

As commercially available active ester hardeners, examples of active ester compounds containing a dicyclopentadiene-type diphenol structure include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", and "HPC". -8000H-65TM", "EXB-8000L-65TM", "EXB-8150-65T" (manufactured by DIC Corporation), and examples of the active ester compound containing a naphthalene structure include "EXB9416-70BK" (manufactured by DIC Corporation). Examples of the active ester compound containing the acetyl compound of phenol novolac include "DC808" (manufactured by Mitsubishi Chemical Corporation), and examples of the active ester compound containing the benzyl compound of phenol novolac include "YLH1026" (manufactured by Mitsubishi Chemical Corporation). (manufactured by Mitsubishi Chemical Corporation). Examples of the active ester-based hardener that is the acetyl compound of phenol novolac include "DC808" (manufactured by Mitsubishi Chemical Corporation). Examples of the benzyl compound of phenol novolac, that is, the active ester-based hardener are " YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation), etc.

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 cyanate-based hardeners include bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4,4' -Methylene bis(2,6-dimethylphenyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2- Bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1, 3-Bis(4-cyanatophenyl-1-(methylethylene))benzene, bis(4-cyanatephenyl)sulfide and bis(4-cyanatephenyl)ether, etc. 2-functional cyanate ester resin, polyfunctional cyanate ester resin derived from phenol novolac and cresol novolac, etc., prepolymers in which part of these cyanate ester resins are triazinized, etc. Specific examples of cyanate ester-based hardeners include "PT30" and "PT60" (phenol novolak type polyfunctional cyanate ester resin), "ULL-950S" (polyfunctional cyanate ester resin) manufactured by Lonza Japan Co., Ltd. ), "BA230", "BA230S75" (a prepolymer in which part or all of bisphenol A dicyanate is triazinized terpolymer), etc.

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

The amount ratio of epoxy resin and hardener is the ratio of [the total number of epoxy groups of the epoxy resin]: [the total number of reactive groups of the hardener], preferably in the range of 1:0.01 to 1:2, more preferably in the range of 1:0.01 to 1:2. The best range is 1:0.05~1:1.5, and the even better range is 1:0.1~1:1. Here, the reactive groups of the curing agent include active hydroxyl groups, active ester groups, etc., and vary depending on the type of the curing agent. In addition, the total number of epoxy groups of the epoxy resin is a value obtained by dividing the solid mass of each epoxy resin by the epoxy group equivalent for all epoxy resins. The so-called reactive groups of the hardener are The total is the sum of the solid content mass of each hardener divided by the reactive group equivalent for all hardeners. By setting the ratio of the epoxy resin to the hardener in this range, the heat resistance of the hardened material 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 contains a mixture of a liquid epoxy resin and a solid epoxy resin as (A) epoxy resin, and (B) a hardener selected from a phenol-based hardener, a naphthol-based hardener, One or more types from the group consisting of active ester hardeners and cyanate ester hardeners. As (A) epoxy resin, the mass ratio of the mixture of liquid epoxy resin and solid epoxy resin (liquid epoxy resin: solid epoxy resin) is preferably 1:0.1 to 1:20, more preferably 1:1～1:10, and even better is 1:5～1:8. (B) The hardener preferably contains one or more types selected from the group consisting of a phenol-based hardener, a naphthol-based hardener, an active ester-based hardener, and a cyanate ester-based hardener, and more preferably Contains at least one selected from the group consisting of phenolic hardeners and active ester hardeners.

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

The content ratio of the active ester-based hardener relative to the entire component (B) is preferably 40 mass% or more, more preferably 50 mass% or more, and still more preferably 60 mass% based on 100 mass% of the (B) component. %above. The upper limit is preferably 75 mass% or less, more preferably 73 mass% or less, and still more preferably 70 mass% or less. By containing the active ester-based hardener so as to fall within this range, it becomes easy to adjust the transmission coefficient P within the specified range.

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

-(C) Inorganic filler- In one embodiment, the resin composition may contain an inorganic filler. The material of the inorganic filler is not particularly limited, but examples include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, Diaspore, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate , bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate and zirconium tungstate phosphate, etc. Among these, silicon dioxide is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, and the like. Moreover, as silica, spherical silica is preferable. One type of inorganic filler can be used alone, or two or more types can be used in combination.

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

The average particle size of the inorganic filler can be measured by the laser diffraction and scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis using a laser diffraction and scattering particle size distribution measuring device, and the median diameter can be measured as the average particle diameter. As a measurement sample, it is preferable to use one in which an inorganic filler is dispersed in methyl ethyl ketone by ultrasonic waves. As a laser diffraction scattering particle size distribution measuring device, "LA-500" manufactured by Horiba Manufacturing Co., Ltd., "SALD-2200" manufactured by Shimadzu Corporation, etc. 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 still 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, still more preferably 40 m ² /g or less. The specific surface area of the inorganic filler can be measured using, for example, a BET fully automatic specific surface area measuring device. More specifically, the specific surface area is obtained by adsorbing nitrogen gas on the surface of a sample using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Corporation) according to the BET method, and calculating the specific surface area using the BET multi-point method.

From the viewpoint of improving moisture resistance and dispersibility, the inorganic filler is preferably a fluorine-containing silane coupling agent, an aminosilane coupling agent, an epoxysilane coupling agent, a mercaptosilane coupling agent, or a silane coupling agent. Coupling agent, alkoxysilane compound, organosilazane compound, titanate coupling agent, etc., and treatment with one or more surface treatment agents. Treatment with aminosilane coupling agent is particularly preferred. Examples of commercially available surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industries, Ltd. and "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industries, Ltd. Oxysilane), "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Industries, Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industries, Ltd. Silane), "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Industries, Ltd., "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industries, Ltd., "KBM-4803" manufactured by Shin-Etsu Chemical Industries, Ltd. (Long-chain epoxy silane coupling agent), "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., etc.

From the perspective of improving the dispersibility of the inorganic filler by the degree of surface treatment with the surface treatment agent, it is preferable to use 0.2 to 5 parts by mass of the surface treatment agent based on 100 parts by mass of the component (C). , it is better to use 0.2 to 3 parts by mass for surface treatment, and even more preferably to use 0.3 to 2 parts by mass for surface treatment.

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 material. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m ² or more, more preferably 0.1 mg/m ² or more, 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 sheet form, 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 amount of carbon per unit surface area of the inorganic filler can be determined by cleaning the surface-treated inorganic filler with a solvent (such as methyl ethyl ketone (MEK)). Specifically, as a solvent, a sufficient amount of MEK is added to the inorganic filler surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25° C. for 5 minutes. After removing the supernatant and drying the solid content, a carbon analyzer can be used to measure the amount of carbon per unit surface area of the inorganic filler. As a carbon analyzer, "EMIA-320V" manufactured by Horiba Manufacturing Co., Ltd., etc. can be used.

When the resin composition contains component (C), the content of the inorganic filler is preferably 100% by mass of the non-volatile components in the resin composition from the viewpoint of adjusting the transmission coefficient P within a specified range. It is 40 mass % or more, more preferably 45 mass % or more, still more preferably 50 mass % or more. From the viewpoint of improving insulation performance, adjusting the physical property balance of the resin composition layer, and improving substrate adhesion, the upper limit is preferably 80 mass% or less, more preferably 70 mass% or less, and still more preferably 60 mass%. below or below 55% by mass.

-(D) Thermoplastic resin- In one embodiment, the resin composition may contain (D) thermoplastic resin. Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamide imine resin, polyether imine resin, polyamide resin, Polyurethane resin, polyether polyether resin, polyphenylene ether resin, polycarbonate resin, polyether ether ketone resin, polyester resin, etc., preferably phenoxy resin. Thermoplastic resin can be used individually by 1 type, or in combination of 2 or more types.

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

Examples of the phenoxy resin include those having a skeleton selected from the group consisting of a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a novolak skeleton, a biphenyl skeleton, a fluorine skeleton, and a dicyclopentadiene skeleton. , phenoxy resin with one or more skeletons in the group consisting of norbornene skeleton, naphthalene skeleton, allium 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. Phenoxy resin can be used individually by 1 type, and can also be used in combination of 2 or more types. Specific examples of phenoxy resins include "1256" and "4250" manufactured by Mitsubishi Chemical Corporation (both phenoxy resins containing a bisphenol A skeleton), and "YX8100" (phenoxy resins containing a bisphenol S skeleton). base resin) and "YX6954" (phenoxy resin containing a bisphenol acetophenone skeleton). Others include "FX280" and "FX293" manufactured by Nippon Steel and Sumitomo Metal Chemical Co., Ltd., and "YL7500BH30" manufactured by Mitsubishi Chemical Corporation. , "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290" and "YL7482", etc.

Examples of the polyvinyl acetal resin include polyvinyl methyl resin and polyvinyl butyral resin, and polyvinyl butyral resin is preferred. Specific examples of the polyvinyl acetal resin include "Denka butyral 4000-2", "Denka butyral 5000-A", "Denka butyral 6000-C" and "Denka butyral 6000-EP" manufactured by Denka Chemical Industry 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 Co., Ltd.

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

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

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

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

Among them, as the thermoplastic resin, phenoxy resin and polyvinyl acetal resin are preferred. Accordingly, in a suitable embodiment, the thermoplastic resin includes at least one selected from the group consisting of phenoxy resin and 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 with a weight average molecular weight of 40,000 or more, the transmission coefficient P is lowered, and the surface roughness can be stabilized even if the thickness of the insulating layer becomes thinner.

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

-(E) Hardening accelerator- 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, metal-based hardening accelerators, etc. Preferred are phosphorus-based hardening accelerators and amine-based hardening accelerators. Hardening accelerator, imidazole type hardening accelerator, metal type hardening accelerator, more preferably amine type hardening accelerator, imidazole type hardening accelerator, metal type 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, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, etc., preferably triphenylphosphine and tetrabutylphosphonium Decanoate.

Examples of the amine-based hardening accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, and 2,4,6-aminoglycan. (dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc., preferably 4-dimethylaminopyridine, 1,8-di 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-diamino -6-[2'-Undecyl imidazolyl-(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-triazineiso 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]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazole Among imidazole compounds such as phosphine and 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins, 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferred.

As the imidazole hardening accelerator, commercially available products can be used, 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, dimethyl 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1 ,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide, etc., preferred It is dicyandiamide, 1,5,7-triazabicyclo[4.4.0]dec-5-ene.

Examples of metal-based hardening accelerators include organic metal complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organic metal complex include organic cobalt complexes such as cobalt (II) acetylpyruvate and cobalt (III) acetylpyruvate, and organic copper complexes such as copper (II) acetylpyruvate. Compounds, organic zinc complexes such as zinc(II) acetylpyruvate, organic iron complexes such as iron(III) acetylpyruvate, organic nickel complexes such as nickel(II) acetylpyruvate , organic manganese complexes such as manganese (II) acetylpyruvate, etc. Examples of organic metal salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and the like.

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

-(F) Flame retardant- In one embodiment, the resin composition may contain (F) flame retardant. Examples of the flame retardant include organic phosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, polysiloxane flame retardants, metal hydroxides, and the like. One type of flame retardant can be used alone, or two or more types can be used in combination.

As the flame retardant, commercially available products can be used, and examples thereof include "HCA-HQ" manufactured by Sanko Co., Ltd. and "PX-200" manufactured by Daihachi Chemical Industry Co., Ltd. As the flame retardant, one that is difficult to hydrolyze is preferred, for example, 10-(2,5-dihydroxyphenyl)-10-hydrogen-9-oxa-10-phosphaphenanthrene (Phosphaphenanthrene)-10-oxidation is preferred. Things etc.

When the resin composition contains a flame retardant, the content of the flame retardant is preferably 0.5 mass % to 20 mass %, and more preferably 0.5 mass % to 15 mass %, assuming that the non-volatile components in the resin composition are 100 mass %. %, more preferably 0.5 mass% to 10 mass%.

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

As the rubber particles, commercially available products can be used, and examples thereof include "EXL2655" manufactured by Dow Chemical Japan, "AC3401N" and "AC3816N" manufactured by Aika Industrial Co., Ltd., and the like.

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

-(H) Optional additives- In one embodiment, the resin composition may further contain 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. As well as resin additives such as tackifiers, defoaming agents, leveling agents, adhesion-imparting agents and colorants.

<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 then at 180°C for 30 minutes will vary depending on the balance of the physical properties of the resin composition. From the viewpoint of good adhesion to the substrate, 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 the transmission coefficient P is 5cc/ ^m2 ·mm from the viewpoint of suppressing the oxidation of the metal such as copper foil as the base of the insulating layer and improving the adhesion to the base because it is difficult for oxygen to pass through the insulating layer. ^-1・day・atom or less, preferably 4.5cc/m ²・mm ^-1・day・atom or less, more preferably 4cc/m ²・mm ^-1・day・atom or less. The transmission coefficient P can be within this range by adjusting the contents of the hardener, inorganic filler, thermoplastic resin, etc., for example. The transmission coefficient P can be measured according to the description of <Measurement of oxygen transmission rate and transmission coefficient> described later.

The oxygen transmittance of the cured product obtained by thermally curing the resin composition layer at 100°C for 30 minutes and then at 180°C for 30 minutes. When the thickness of the cured product was measured as 60 μm, the balance of the physical properties of the resin composition easily changed. From the perspective of good adhesion to the substrate, it is preferably 20cc/m ²・day・atom or more, more preferably 25cc/m ²・day・atom or more, and still more preferably 30cc/m ²・day・Atom or above. The upper limit of the oxygen transmittance is because it is difficult for oxygen to pass through the insulating layer. As a result, from the viewpoint of suppressing oxidation of the metal such as copper foil as the base of the insulating layer and improving the adhesion to the base, 80cc/ ^m2・Day・atom or less, preferably 75cc/m ²・day・atom or less, still more preferably 70cc/m ²・day・atom or less. The oxygen permeability can be measured according to the description of <Measurement of oxygen permeability and permeability coefficient> described below.

The cured product obtained by thermally curing the resin composition layer at 100°C for 30 minutes and then at 180°C for 30 minutes has a transmission coefficient P of 1.2cc/m ²・mm ^-1・day・atom or more than 5cc/m ²・mm ^-1・day・atom or less, showing excellent peeling strength (adhesion to substrate) with copper foil. That is, an insulating layer with excellent base adhesion is provided. As for the substrate adhesion, the load required to peel off a small piece with a width of 10 mm is preferably 0.2kgf or more, more preferably 0.25kgf or more, and still more preferably 0.3kgf or more. The upper limit may be preferably 1kgf or less, 10kgf or less, etc. The substrate adhesion can be measured according to the description of <Measurement of substrate adhesion> described below.

The cured product obtained by thermally curing the resin composition layer at 100°C for 30 minutes and then at 180°C for 30 minutes shows excellent reflow resistance. That is, an insulating layer with excellent reflow resistance is provided. Even if the insulating layer formed using the resin composition layer is subjected to a reflow step that reproduces the reflow temperature with 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, and it is more preferable that there is no insulating layer. Peeling from conductor layers. Reflow resistance can be evaluated according to the method described in <Evaluation of Reflow Resistance> described later.

Even if the resin composition layer of the present invention is as thin as 15 μm or less, it can provide an insulating layer (hardened product of the resin composition layer) with 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 component. For example, it can be suitably used as a resin composition for forming wiring by a semi-additive process (a semi-additive process by a semi-additive process). Used for wiring formation) resin composition. Furthermore, 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 suitably used as an interlayer insulation for forming a printed circuit board. The resin composition layer of the layer (the resin composition layer for the interlayer insulating layer of the printed circuit board) is used.

Furthermore, 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 also be suitably used. For example, it can also be suitably used as a resin composition for sealing a semiconductor wafer (a 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 films, metal foils, and release papers made of plastic materials, and films and metal foils made of plastic materials are preferred.

When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes referred to as "PET"), polyethylene naphthalate (hereinafter referred to as "PET"), and polyethylene naphthalate (hereinafter referred to as "PET"). Polyesters such as (sometimes referred to as "PEN"), polycarbonates (hereinafter sometimes referred to as "PC"), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, and triacetyl fibers (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and cheap polyethylene terephthalate is particularly preferred.

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

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

Furthermore, as the support, a release layer-attached support having a release layer can be used on the surface bonded to the resin composition layer. Examples of the release agent used in the release layer of the support with the release layer include those selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and polysiloxane resins. More than 1 type of release agent. As the support with the release layer, commercially available products can be used. For example, PET films having a release layer containing an alkyd resin release agent as a main component, such as "SK-1" and "AL" manufactured by Lintec Corporation, can be used. -5", "AL-7", "Lumirror T60" made by Toray, "Purex" made by Teijin, "Unipiel" made by Unitika, etc.

Although the thickness of the support is not particularly limited, it is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. Furthermore, when using a support with a release layer, it is preferable that the thickness of the entire support with a release layer is within the above range.

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

The resin sheet can be produced, for example, by preparing a resin varnish in which a resin composition is dissolved in an organic solvent, applying the resin varnish on a support using a die coater, 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), and cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and Acetate esters such as carbitol acetate, carbitols such as cellosolve and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethyl formamide, dimethyl ethyl Amide solvents such as amide (DMAc) and N-methylpyrrolidone. One type of organic solvent may be used alone, or two or more types may be used in combination.

Drying can be carried out by known methods such as heating and hot air blowing. 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, 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 using a resin varnish containing 30% to 60% by mass of an organic solvent, the resin can be formed by drying at 50°C to 150°C for 3 to 10 minutes. composition layer.

Resin sheets can be rolled into rolls and stored. When the resin sheet has a protective film, it can be used by peeling off 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) epoxy resin and (B) hardener. The thickness is 15 μm or less. The transmission coefficient of the cured product is obtained by thermal curing at 100°C for 30 minutes and then at 180°C for 30 minutes. P is the cured product of the resin composition layer of 1.2cc/m ²・mm ^-1・day・atom or more and 5cc/m ²・mm ^-1・day・atom or less. The insulating layer is provided between the first conductor layer and the second conductor layer to insulate the first conductor layer and the second conductor layer (the conductor layer is sometimes called 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, still more preferably 5 μm or less. The lower limit is not particularly limited, but may be 0.1 μm or more. The so-called distance between the first conductor layer and the second conductor layer (the thickness of the insulation layer between the first and second conductor layers) refers to the main surface 11 of the first conductor layer 1 and the second conductor layer as shown in Figure 1. The thickness t1 of the insulating layer 3 between the main surfaces 21 of 2. The first and second conductor layers are adjacent conductor layers through the insulating layer, and the main surface 11 and the main surface 21 face each other.

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

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

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

The inner layer substrate and the resin sheet can be laminated, for example, by heating and pressing the resin sheet to the inner layer substrate from the support side. Examples of a member for heat and pressure bonding the resin sheet to the inner substrate (hereinafter also referred to as "heat and pressure bonding member") include a heated metal plate (SUS mirror plate, etc.) or a metal roller (SUS roller). Still, it is preferable not to directly punch the heating and pressing member onto the resin sheet, but to punch through an elastic material such as heat-resistant rubber so that the surface irregularities of the inner substrate fully follow the resin sheet.

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

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

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

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

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

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

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

When manufacturing a printed circuit board, the steps of (III) drilling holes in the insulating layer, (IV) roughening the insulating layer, and (V) forming the conductor layer may be further performed. These steps (III) to step (V) can be implemented according to various well-known methods for those with ordinary knowledge in the field of the present invention used in the manufacture of printed circuit boards. Furthermore, when the support is removed after step (II), the support can be removed between step (II) and step (III), between step (III) and step (IV), or between step (IV). and between steps (V). In addition, if necessary, the formation of the insulating layer and the conductor layer in steps (II) to (V) can be repeated to form a multilayer wiring board. In this case, it is preferable that the thickness of the insulating layer between 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 through holes, through holes, etc. in the insulating layer. Step (III) may be implemented using a drill, laser, plasma, etc., depending on the composition of the resin composition used to form 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 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 can be roughened in the order of swelling treatment with a swelling liquid, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing liquid. The swelling liquid used in the roughening treatment is not particularly limited, but examples thereof include alkaline solutions, surfactant solutions, etc., and an alkali solution is preferred. As the alkali solution, a sodium hydroxide solution and potassium hydroxide solution are more preferred. solution. Examples of commercially available swelling solutions include "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by Atotech Japan. Although the swelling treatment by the swelling liquid is not particularly limited, it can be performed by immersing the insulating layer in a swelling liquid of 30° C. to 90° C. for 1 minute to 20 minutes, for example. 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 of 40°C to 80°C for 5 to 15 minutes. The oxidizing agent used in the roughening treatment is not particularly limited, but may be, for example, an alkaline permanganic acid solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment by an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60°C to 80°C for 10 to 30 minutes. Moreover, the concentration of permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as "Concentrate Compact CP" and "Dosing solution Securiganth P" manufactured by Atotech Japan. In addition, the neutralizing liquid used in the roughening treatment is preferably an acidic aqueous solution. An example of a commercially available product is "Reduction solution Securigant P" manufactured by Atotech Japan. The treatment with the neutralizing liquid can be performed by immersing the treated surface roughened by the oxidizing agent in the neutralizing liquid at 30° C. to 80° C. for 5 to 30 minutes. From the viewpoint of workability and the like, a method in which the object roughened by an oxidizing agent is immersed in a neutralizing liquid at 40° C. to 70° C. for 5 to 20 minutes is preferred.

In one embodiment, the arithmetic mean roughness (Ra) of the surface of the insulating layer after roughening 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. In addition, the root mean square roughness (Rq) of the surface of the insulating layer after roughening 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 mean roughness (Ra) and root mean square roughness (Rq) of the insulation layer surface can be measured using a non-contact surface roughness meter.

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

The conductor material used for the conductor 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. The above metals. The conductor layer may be a single metal layer or an alloy layer. Examples of the alloy layer include alloys of two or more metals selected from the above groups (such as nickel-chromium alloys, copper-nickel alloys, and copper-titanium alloys). ) formed by the layer. Among them, from the viewpoint of versatility, cost, ease of patterning, etc. of forming the conductor layer, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper or nickel is preferred.・Alloy layer of chromium alloy, copper-nickel alloy, copper-titanium alloy, more preferably single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper or alloy layer of nickel-chromium alloy, Even better is a single metal layer of copper.

The conductor layer can be a single-layer structure or a multi-layer structure in which two or more single metal layers or alloy layers composed of different types 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 nickel-chromium alloy.

The thickness of the conductor layer varies depending on the desired design of the printed circuit board, but is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

In one embodiment, the conductor layer may be formed by plating. For example, the surface of the insulating layer can be plated by conventionally known techniques such as semi-additive method and full-additive method to form a conductor layer with a desired wiring pattern. From the viewpoint of simplicity of manufacturing, it is preferable to Formed by semi-additive method. The following shows an example in which the conductor layer is formed by a semi-additive method.

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Then, on the formed plating seed crystal layer, a mask pattern exposing a part of the plating seed crystal layer is formed corresponding to the 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 with a desired wiring pattern.

Since the resin sheet of the present invention provides an insulating layer with good embedding properties for components, it can also be suitably used in printed circuit boards where components have built-in circuit boards. The component's built-in circuit board can be manufactured by well-known manufacturing methods.

A printed circuit board manufactured using the resin sheet of the present invention may have an insulating layer, which 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 semiconductor devices include various semiconductor devices used in electrical products (such as computers, mobile phones, digital cameras, and televisions) and vehicles (such as motorcycles, cars, trains, ships, and aircraft).

The semiconductor device of the present invention can be manufactured by mounting components (semiconductor chips) on conductive portions of a printed circuit board. The so-called "conduction point" refers to "the place where electrical signals are transmitted on the printed circuit board." This place can be the surface or an embedded place, it doesn't matter. In addition, the semiconductor wafer is not particularly limited as long as it is an electrical circuit element using a semiconductor as a material.

The mounting method of the semiconductor chip when manufacturing the semiconductor device is not particularly limited as long as the semiconductor chip functions effectively. However, specific examples include wire bonding mounting method, flip chip mounting method, and non-concave/convex mounting method. The mounting method of build-up layer (BBUL), the mounting method of anisotropic conductive film (ACF), the mounting method of non-conductive film (NCF), etc. Here, the so-called "mounting method by uneven build-up layer (BBUL)" is "a mounting method in which the semiconductor chip is directly embedded in the recessed portion of the printed circuit board and the semiconductor chip is connected to the wiring on the printed circuit board." [Example]

Hereinafter, the present invention will be explained in detail through examples. The present invention is not limited to these embodiments. However, in the following, "parts" and "%" expressing amounts mean "parts by mass" and "% by mass" respectively, unless otherwise clearly stated.

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

<Measurement of the specific surface area of the inorganic filler> By using a BET fully automatic specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Corporation), nitrogen gas is adsorbed on the surface of the sample, and the specific surface area is calculated using the BET multi-point method, and the inorganic filler is measured. The specific surface area.

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

<Preparation of Resin Composition 1> 6 parts of benzoxylenol-type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight: approximately 185), naphthalene-type epoxy resin (manufactured by Nippon Steel & Sumitomo Metal Chemical Corporation) "ESN475V", epoxy equivalent weight: approximately 332) 5 parts, bisphenol AF type epoxy resin (Mitsubishi Chemical Corporation "YL7760", epoxy equivalent weight: approximately 238) 15 parts, cyclohexane type epoxy resin (Mitsubishi Chemical 2 parts of "ZX1658GS" manufactured by the company, epoxy equivalent (approximately 135), phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, 30 mass% solid content of cyclohexanone: 1 part of methyl ethyl ketone (MEK): 1 solution, Mw=35000), stir in a mixed solvent of 20 parts naphtha and 10 parts cyclohexanone while heating to 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 approximately 151, and a solid content of 50% 2-methoxypropanol was mixed). solution), 4 parts of active ester hardener ("EXB-8150-65T" manufactured by DIC Corporation, toluene solution with an active group equivalent of approximately 229 and non-volatile content of 65% by mass), 6 parts of inorganic filler, 150 parts of amine type 0.05 part of the hardening accelerator (4-dimethylaminopyridine (DMAP)) was uniformly dispersed with a high-speed rotary mixer, and then filtered with a filter cartridge ("SHP020" manufactured by ROKITECHNO) to prepare resin composition 1.

<Preparation of Resin Composition 2> 6 parts of benzoxylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight: about 185), naphthalene type epoxy resin (manufactured by Nippon Steel & Sumitomo Metal Chemical Company) "ESN475V", epoxy equivalent weight: approximately 332) 5 parts, bisphenol AF type epoxy resin (Mitsubishi Chemical Corporation "YL7760", epoxy equivalent weight: approximately 238) 15 parts, bisphenol AF type epoxy resin (Nippon Steel "ZX1059" manufactured by Sumitomo Chemical Co., Ltd., epoxy group equivalent approximately 169, 1:1 mixture of bisphenol A type and bisphenol F type) 4 parts, naphthyl ether type epoxy resin ("EXA-7311 manufactured by DIC Corporation" -G4", 2 parts of epoxy equivalent (approximately 213), phenoxy resin ("YL7500BH30" manufactured by Mitsubishi Chemical Corporation, 30 mass% solid content: 1:1 solution of cyclohexanone: methyl ethyl ketone (MEK) , Mw=44000) 2 parts, stir and heat to dissolve in a mixed solvent of 20 parts naphtha and 10 parts cyclohexanone. 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 approximately 151, and a solid content of 50% 2-methoxypropanol was mixed). Solution) 4 parts, active ester hardener ("EXB-8000L-65M" manufactured by DIC Corporation, MEK solution with an active group equivalent of about 220 and non-volatile content 65% by mass) 6 parts, 1 40 parts of inorganic filler, amine type 0.05 part of the hardening accelerator (4-dimethylaminopyridine (DMAP)) was uniformly dispersed with a high-speed rotary mixer, and then filtered with a filter cartridge ("SHP020" manufactured by ROKITECHNO) to prepare resin composition 2.

<Preparation of Resin Composition 3> 6 parts of benzoxylenol-type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight: about 185), naphthalene-type epoxy resin (manufactured by Nippon Steel & Sumitomo Metal Chemical Corporation) "ESN475V", epoxy equivalent weight: approximately 332) 5 parts, bisphenol AF type epoxy resin (Mitsubishi Chemical Corporation "YL7760", epoxy equivalent weight: approximately 238) 15 parts, bisphenol AF type epoxy resin (Nippon Steel "ZX1059" manufactured by Sumitomo Chemical Co., Ltd., epoxy group equivalent approximately 169, 1:1 mixture of bisphenol A type and bisphenol F type) 4 parts, naphthyl ether type epoxy resin ("EXA-7311 manufactured by DIC Corporation" -G4", 2 parts of epoxy equivalent (approximately 213), phenoxy resin ("YL7500BH30" manufactured by Mitsubishi Chemical Corporation, 30 mass% solid content: 1:1 solution of cyclohexanone: methyl ethyl ketone (MEK) , Mw=44000) 2 parts, stir and heat to dissolve in a mixed solvent of 20 parts naphtha and 10 parts cyclohexanone. 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 approximately 151, and a solid content of 50% 2-methoxypropanol was mixed). Solution) 4 parts, active ester hardener ("EXB-8000L-65M" manufactured by DIC Corporation, MEK solution with an active group equivalent of about 220 and non-volatile content 65% by mass), 12 parts, 1 40 parts of inorganic filler, amine type 0.05 part of the hardening accelerator (4-dimethylaminopyridine (DMAP)) was uniformly dispersed with a high-speed rotary mixer, and then filtered with a filter cartridge ("SHP020" manufactured by ROKITECHNO) to prepare resin composition 3.

<Preparation of Resin Composition 4> 6 parts of benzoxylenol-type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight: approximately 185), naphthalene-type epoxy resin (manufactured by Nippon Steel & Sumitomo Metal Chemical Corporation) "ESN475V", epoxy equivalent weight: approximately 332) 5 parts, bisphenol AF type epoxy resin (Mitsubishi Chemical Corporation "YL7760", epoxy equivalent weight: approximately 238) 15 parts, cyclohexane type epoxy resin (Mitsubishi Chemical 2 parts of "ZX1658GS" manufactured by the company, epoxy equivalent (approximately 135), phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, 30 mass% solid content of cyclohexanone: 1 part of methyl ethyl ketone (MEK): 1 solution), stir and heat to dissolve in a mixed solvent of 20 parts naphtha and 10 parts cyclohexanone. 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 approximately 151, and a solid content of 50% 2-methoxypropanol was mixed). Solution) 4 parts, active ester hardener (MEK solution "EXB-8000L-65M" manufactured by DIC Corporation, active group equivalent weight approximately 220, non-volatile content 65 mass%) 6 parts, inorganic filler 2 160 parts, amine type 0.05 part of the hardening accelerator (4-dimethylaminopyridine (DMAP)) was uniformly dispersed with a high-speed rotary mixer, and then filtered with a filter cartridge ("SHP020" manufactured by ROKITECHNO) to prepare resin composition 4.

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

<Preparation of resin sheet> As a support, prepare a PET film ("Lumirror R80" manufactured by Toray Industries, thickness 38 μm) that has been released with an alkyd resin release agent ("AL-5" manufactured by Lintec Corporation). Softening point 130℃, "release PET").

By applying each resin composition on the release PET, apply it uniformly on the mold coater so that the thickness of the dried resin composition layer becomes 10 μm, dry it at 70°C to 95°C for 2 minutes, and then release it from the mold. A resin composition layer was obtained on PET. Next, as a protective film, the 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 on the surface that was not bonded to the support of the resin sheet. Perform lamination. Thereby, a resin sheet A composed of release PET (support), a resin composition layer, and a protective film was obtained in this order. Furthermore, resin sheet B was obtained in the same manner as resin sheet A except that each resin composition was uniformly coated with a die coater so that the thickness of the dried resin composition layer became 30 μm.

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

<Evaluation of reflow resistance> - Preparation of evaluation substrate A - (1) Copper-clad laminate As a copper-clad laminate, a glass cloth base material epoxy resin double-sided copper-clad laminate prepared with a copper foil layer laminated on both sides ( Copper foil thickness 3μm, substrate thickness 0.15mm, "HL832NSF LCA" manufactured by Mitsubishi Gas Chemical Co., Ltd., 255×340mm size).

(2) Lamination of resin sheets The protective film was peeled off from each resin sheet A produced in Examples and Comparative Examples, and a batch-type vacuum pressure laminator (manufactured by Nikko Materials Co., Ltd., 2-stage stacking laminator, CVP700) was used. The resin composition layer is bonded to the copper-clad laminate and laminated on both sides of the copper-clad laminate. Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then 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. Put the copper-clad laminate laminated with resin sheets into an oven at 100°C and heat-harden it for 30 minutes. Then transfer it to an oven at 180°C and heat-harden it for 30 minutes to form an insulating layer and peel it off. Mold PET. Let this be the hardened substrate A.

(4) The step of roughening treatment: Perform desmear treatment as a roughening treatment on the insulating layer of the hardened substrate A. Still, as a desmear treatment, perform the following wet desmear treatment.

Wet desmear treatment: Immerse in the 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 the oxidant solution ( "Concentrate Compact CP" manufactured by Atotech Japan, an aqueous solution with a potassium permanganate concentration of approximately 6% and a sodium hydroxide concentration of approximately 4%) was immersed at 80°C for 20 minutes, and finally immersed in a neutralizing 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. Let this be roughened substrate A.

(5) Step of forming the conductor layer (5-1) Electroless plating step In order to form the conductor layer on the surface of the insulating layer of the roughened substrate A, a plating step including the following steps 1 to 6 is performed (using Atotech Japan Co., Ltd. The 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 with through holes) Use Cleaning Cleaner Securiganth 902 (trade name) to clean the surface of the roughened substrate A at 60°C for 5 minutes. 2. Soft etching (cleaning in the through hole): Use sulfuric acid acid sodium peroxodisulfate aqueous solution on the surface of the roughened substrate A at 30°C for 1 minute. 3. Pre-dip (to adjust the charge given to the surface of the Pd insulating layer). Use Pre. Dip Neoganth B (trade name) on the surface of the roughened substrate A and treat it at room temperature for 1 minute. 4. Accelerator application (application of Pd to the surface of the insulating layer) The surface of the roughened substrate A was treated with Activator Neoganth 834 (trade name) at 35°C for 5 minutes. 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 (precipitate Cu on the surface of the insulating layer (Pd surface)). Use Basic Solution Printganth MSK-DK (trade name), Copper solution Printganth MSK (trade name), and Copper solution Printganth MSK (trade name) to roughen the surface of the substrate A. Treat the mixture with Stabilizer Printganth MSK-DK (trade name) and Reducer Cu (trade name) at 35°C for 15 minutes. The thickness of the electroless copper plating layer formed 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 of the electroless copper plating layer and the electroless copper plating layer is approximately 15 μm). This is designated as evaluation substrate A.

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

<Measurement of base adhesion> (1) Base treatment of copper foil: The glossy side of "3EC-III" (electrical copper foil, 35 μm) manufactured by Mitsui Metal Mining Co., Ltd. was immersed in Mec etch bond "CZ-8101" manufactured by Mec Corporation , roughen the copper surface (Ra value = 1μm), and implement anti-rust treatment (CL8300). This copper foil is called CZ copper foil. Furthermore, it was heated in an oven at 130° C. for 30 minutes.

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

(3) Determination of copper foil peeling strength (substrate adhesion) Cut the prepared sample into small pieces of 150×30mm. Use a cutter on the copper foil part of the small piece, put in a section of 10mm width and 100mm length, peel off one end of the copper foil, and hold it with a clamp (Autocom type testing machine, "AC-50C-SL" made by T.S.Y Co., Ltd.) Using an Instron universal testing machine, the load when peeling 35mm in the vertical direction at a speed of 50mm/min at room temperature is measured in accordance with JIS C6481, and evaluated using the following standards. Evaluation criteria ○: The measurement result of substrate adhesion is 0.2kgf or more ×: The measurement result of substrate adhesion is less than 0.2kgf

<Measurement of oxygen transmittance and transmission coefficient> - Preparation of hardened sheets - The protective film was peeled off from each resin sheet B produced in Examples and Comparative Examples, and a batch-type vacuum pressure laminator (manufactured by Nikko Materials Co., Ltd., 2-stage Accumulation laminator, CVP700), laminates two resin sheets B by joining the resin composition layers. Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then 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 the curing conditions of 90° C. and 90 minutes. Then, the release PET on the other side was peeled off to prepare a cured sheet B.

-Measurement of oxygen transmittance and transmission coefficient-Use an oxygen transmittance measuring device (manufactured by MOCON, OX-TRAN2/21) in accordance with JIS-K7126 (isobaric method) in an environment of 23°C, 0%RH and 23 Under the environment of ℃ and 90%RH, measure the oxygen transmittance of the hardened sheet B. However, the so-called RH system represents relative humidity. Furthermore, by taking the oxygen transmittance of the cured sheet B as a standard and dividing it by the thickness, the transmission coefficient P (oxygen transmission coefficient P) was calculated. The case where the transmittance coefficient P is 5.0cc/m ²・mm ^-1・day・atom or less is evaluated as “○”, and the case where the transmittance coefficient P exceeds 5.0cc/m ²・mm ^-1・day・atom is evaluated as “ ×". In addition, the case where the transmittance coefficient P is 1.2cc/m ²・mm ^-1・day・atom or more is evaluated as “○”, and the case where the transmittance coefficient P is less than 1.2cc/m ²・mm ^-1・day・atom is evaluated as “○”. The evaluation is "×".

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

1‧‧‧The main surface of the first conductor layer 11‧‧‧The main surface of the first conductor layer 2‧‧‧The second conductor layer 21‧‧‧The main surface of the second conductor layer 3‧‧‧Insulation layer t1‧‧‧No.1 The distance between the conductor layer and the second conductor layer (thickness of the insulation 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 (14)

A resin composition layer comprising a resin composition containing (A) epoxy resin, (B) hardener and (C) inorganic filler, characterized in that the thickness of the resin composition layer is 15 μm In the following, the oxygen transmission coefficient of the cured product obtained by thermally curing the resin composition layer at ¹⁰⁰ °C for 30 minutes and then at ¹⁸⁰ °C for 30 minutes when the specific surface area of component (C) is 15 m 2 /g or more and 60 m 2 /g or less P is 1.2cc/m ² ‧mm ^-1 ‧day‧atom and above 5cc/m ² ‧mm ^-1 ‧day‧atom and below. The resin composition layer of claim 1 is formed by wiring using a semi-additive process. The resin composition layer of claim 1, wherein the content of component (C) is 40 mass% or more and 80 mass% or less when the non-volatile components in the resin composition are 100 mass%. The resin composition layer of claim 1, wherein the content of component (B) is 20 mass% or less when the resin component is 100 mass%. The resin composition layer of claim 1, wherein the component (B) contains an active ester hardener. The resin composition layer of claim 5, wherein the content of the active ester hardener is 15 mass% or less when the resin component is 100 mass%. The resin composition layer of claim 1 contains (D) thermoplastic resin. The resin composition layer of Claim 7, wherein the weight average molecular weight of component (D) is 38,000 or more. The resin composition layer of claim 1, wherein the oxygen 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 used to form the insulating layer of a printed circuit board. The resin composition layer of claim 1 is used 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 11 provided on the support. A printed circuit board, which is a printed circuit including a first conductor layer, a second conductor layer and an insulating layer formed between the first conductor layer and the second conductor layer A board, characterized in that the insulating layer is a hardened product of the resin composition layer in any one of claims 1 to 11. A semiconductor device including the printed circuit board of claim 13.