TW201815953A - Resin composition capable of maintaining the contact angle of the surface of a cured product to water by roughening the surface of the cured product - Google Patents

Abstract

To provide a resin composition capable of imparting excellent insulating properties to a thin insulating layer, a resin sheet containing the resin composition, and a printed wiring board and a semiconductor device provided with the thin insulating layer having excellent insulating properties. A resin composition, comprising (A) an epoxy resin and (B) a curing agent, the resin composition is cured by heat at 100 DEG C for 30 minutes and further at 180 DEG C for 30 minutes to obtain a cured product, denote the contact angle of the surface of the cured product to water before the surface of the cured product is roughened as X (DEG), and denote the contact angle of the surface of the cured product to water after the surface of the cured product is roughened as Y (DEG), the relationship of XY ≤ 0 DEG and Y ≥ 80 DEG is satisfied.

Description

   Resin composition   

The present invention relates to a resin composition. Furthermore, it relates to the resin sheet containing this resin composition, a printed wiring board, and a semiconductor device.

In recent years, in order to reduce the size of electronic equipment, printed wiring boards have been made thinner, and the thickness of the inner substrate or the insulating layer has tended to become thinner. As a technique for reducing the thickness of the inner substrate or the insulating layer, for example, a thin film resin composition described in Patent Document 1 is known.

[Prior technical literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2014-152309

In Patent Document 1, the inventors of the present application found that when a thin film is applied to an insulating layer, the thickness becomes larger and the peel strength tends to decrease. In order to solve these problems, it has been proposed to make the blending amount of the thermoplastic resin into a specific amount. method. However, in this document, there is no review of the insulation performance in the case where the thickness of the insulation layer is reduced (hereinafter also referred to as "thin film insulation").

When the insulating layer is a thin film, the inorganic filler particles come into contact with each other and the current transmitted at the interface becomes easy to flow, or because the thickness of the insulating layer is thin, the electrostatic capacitance becomes large and it is easy to short circuit. Insulation becomes harder than before.

An object of the present invention is to provide a resin composition that can provide a thin insulating layer having excellent insulating properties; a resin sheet containing the resin composition; a printed wiring board and a semiconductor device having a thin insulating layer having excellent insulating properties.

As a result of an intensive review in order to solve the aforementioned problems, the inventors of the present case found that the contact angle of water on the surface of the hardened material before the roughening treatment of the hardened material of the resin composition, and the roughening of the hardened material of the resin composition The contact angle of water on the surface of the hardened product after the chemical treatment is within a specific range, the film insulation can be improved, and the present invention has been completed.

That is, the present invention includes the following.

[1] A resin composition containing (A) an epoxy resin and (B) a hardener, and curing the resin composition at 100 ° C for 30 minutes and further at 180 ° C for 30 minutes to obtain a cured product, The contact angle of water on the surface of the hardened material before the roughening treatment is X (°), and the contact angle of water on the surface of the hardened material after roughening the hardened surface is Y (°) In this case, the relationship of XY ≦ 0 ° and Y ≧ 80 ° is satisfied.

[2] The resin composition according to [1] further containing (C) an inorganic filler.

[3] When the non-volatile content in the resin composition is 100% by mass, the content of the component (C) is 50% by mass or more of the resin composition according to [2].

[4] The resin composition according to [2] or [3], wherein the average particle diameter of the component (C) is 0.05 μm to 0.35 μm.

[5] The resin composition according to any one of [1] to [4] containing a fluorine compound.

[6] The fluorine compound is the resin composition according to [5], which is a fluorine-containing epoxy resin.

[7] The fluorine compound is the resin composition according to [5] or [6] of (D) a fluorine-containing silane coupling agent.

[8] The resin composition according to [7], wherein the component (C) is surface-treated with the component (D).

[9] The resin composition according to any one of [1] to [8] for forming an insulating layer of a printed wiring board.

[10] A resin sheet including a support and a resin composition layer formed of the resin composition according to any one of [1] to [9] provided on the support.

[11] The resin sheet according to [10], wherein the thickness of the resin composition layer is 15 m or less.

[12] This insulating layer is formed for a printed wiring board including a first conductor layer, a second conductor layer, and an insulation layer having a thickness of 6 μm or less formed between the first conductor layer and the second conductor layer. [11] The resin sheet described.

[13] A printed wiring board including a first conductor layer, a second conductor layer, and an insulation layer having a thickness of 6 μm or less formed between the first conductor layer and the second conductor layer, and the insulation layer is [1] ~ [9] A printed wiring board comprising a cured product of a resin composition.

[14] A semiconductor device including the printed wiring board according to [13].

According to the present invention, it is possible to provide a resin composition capable of imparting a thin insulating layer having excellent insulating properties; a resin sheet containing the resin composition; a printed wiring board and a semiconductor device having a thin insulating layer having excellent insulating properties.

5‧‧‧ the first conductor layer

51‧‧‧Main surface of the first conductor layer

6‧‧‧ 2nd conductor layer

61‧‧‧Main surface of 2nd conductor layer

7‧‧‧ Insulation

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

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

[Resin composition]

The resin composition of the present invention contains (A) an epoxy resin and (B) a hardener. When the resin composition is cured at 100 ° C. for 30 minutes and further at 180 ° C. for 30 minutes to obtain a cured product, the resin composition is cured. The contact angle of water on the surface of the hardened object before roughening treatment is X (°), and the contact angle of water on the surface of the hardened object after roughening the hardened surface is Y (°) , Satisfy the relationship of XY ≦ 0 ° and Y ≧ 80 °. By adjusting the contact angle X and the contact angle Y so as to satisfy the relationship of XY ≦ 0 ° and Y ≧ 80 °, the surface of the insulating layer is hydrophobicized, so that moisture and the like are difficult to penetrate into the insulating layer, and a thin insulating layer having excellent insulating properties can be provided . Hereinafter, the contact angle with water on the surface of the hardened material before the roughening treatment is performed when the resin composition is cured at 100 ° C for 30 minutes and further at 180 ° C for 30 minutes is referred to as "contact "Angle X" is also referred to as the contact angle of water on the surface of the hardened product after roughening treatment when the hardened product is obtained by curing the resin composition at 100 ° C for 30 minutes and 180 ° C for 30 minutes. "Contact angle Y".

Here, the contact angle refers to a free surface of a stationary liquid, and an angle (taken inside the liquid) between a liquid surface and a solid surface in a place connected to a solid wall.

The resin composition further includes (C) an inorganic filler, (D) a fluorine-containing silane coupling agent, (E) a thermoplastic resin, (F) a hardening accelerator, (G) a flame retardant, and (H) an organic filler as necessary. Additives such as wood may also be used. The resin composition of the present invention is preferably a fluorine-containing compound from the viewpoint of adjusting the contact angle X and the contact angle Y to a desired range. The fluorine compound is a compound containing one or more fluorine atoms per molecule, and is a concept including an organic compound and an inorganic compound. The weight average molecular weight of the fluorine compound is usually 100 to 5,000. The fluorine compound preferably contains any one of the components (A) to (H), and the fluorine compound preferably contains the (A) component and / or the (D) component. A fluorine compound may be used individually by 1 type, and may be used in combination of 2 or more type. When the fluorine compound contains the component (A), the component (A) may be a combination of a fluorine compound and a non-fluorine compound (A) component. Hereinafter, each component contained in the resin composition of this invention is demonstrated in detail.

<(A) epoxy resin>

(A) Examples of the epoxy resin include fluorinated epoxy resins such as bisphenol AF-type epoxy resins and perfluoroalkyl-type epoxy resins, bisphenol A-type epoxy resins, and bisphenol F-type epoxy resins. Resin, bisphenol S epoxy resin, dicyclopentadiene epoxy resin, triphenol epoxy resin, naphthol novolac epoxy resin, phenol novolac epoxy resin, tert-butyl-catechol Epoxy resin, naphthalene epoxy resin, naphthol epoxy resin, anthracene epoxy resin, glycidylamine epoxy resin, glycidyl ester epoxy resin, cresol novolac ring Oxygen resin, biphenyl epoxy resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, epoxy resin containing spiro ring, Cyclohexanedimethanol epoxy resin, anisole epoxy resin, trimethylol epoxy resin, tetraphenylethane epoxy resin, etc. An epoxy resin may be used individually by 1 type, and may use 2 or more types together.

The epoxy resin is preferably an epoxy resin having two or more epoxy groups in one molecule. When the non-volatile content of the epoxy resin is 100% by mass (hereinafter, also referred to simply as "mass%"), at least 50% by mass or more is preferably an epoxy resin having two or more epoxy groups in one molecule. Among them, epoxy resins having two or more epoxy groups in one molecule and being liquid at a temperature of 20 ° C (hereinafter referred to as "liquid epoxy resins") and three or more epoxy groups in one molecule are included. A solid epoxy resin (hereinafter referred to as "solid epoxy resin") at a temperature of 20 ° C is preferred. By using a liquid epoxy resin and a solid epoxy resin in combination as the epoxy resin, excellent flexibility can be obtained, and the fracture strength of the cured product is also improved.

As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester epoxy resin, and glycidyl amine type ring are used. Oxygen resin, phenol novolac epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexanedimethanol epoxy resin, glycidylamine epoxy resin, and epoxy resin with butadiene structure are Among them, glycidylamine type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, and naphthalene type epoxy resin are more preferable. Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene-type epoxy resin) manufactured by DIC, "828US", "jER828EL" (double Phenol A type epoxy resin), "jER807" (bisphenol F type epoxy resin), "jER152" (phenol novolac type epoxy resin), "630", "630LSD" (glycidylamine type epoxy resin), "ZX1059" (mixed product of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., and "YD-8125G" (bisphenol A type) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. Epoxy resin), "EX-721" (glycidyl ester epoxy resin) manufactured by Nagase Chemtex, "Celloxide 2021P" (alicyclic epoxy resin with ester skeleton) manufactured by Daicel, "PB-3600 "(Epoxy resin with butadiene structure)," ZX1658 "manufactured by Nippon Steel Chemical Co., Ltd.," ZX1658GS "(liquid 1,4-glycidylcyclohexane), and" 630LSD "manufactured by Mitsubishi Chemical Corporation ( Glycidylamine type epoxy resin), `` E-7432 '', `` E-7632 '' (Perfluoro Alkyl epoxy resin). These may be used individually by 1 type, and may be used in combination of 2 or more type.

As the solid epoxy resin, a naphthalene type 4-functional epoxy resin, an o-methylphenol novolac type epoxy resin, a dicyclopentadiene type epoxy resin, a triphenol type epoxy resin, a naphthol type epoxy resin, Benzene type epoxy resin, anisole type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, tetraphenylethane type epoxy resin are preferred, naphthalene type 4 functional epoxy resin , Naphthol type epoxy resin, and biphenyl type epoxy resin are more preferable. Specific examples of the solid epoxy resin include "HP4032H" (naphthalene-type epoxy resin), "HP-4700", "HP-4710" (naphthalene-type 4-functional epoxy resin) manufactured by DIC Corporation, "N-690" (o-methylphenol novolac type epoxy resin), "N-695" (o-methylphenol novolac type epoxy resin), "HP-7200", "HP-7200HH", "HP-7200H" ( Dicyclopentadiene type epoxy resin), "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (anisole type epoxy resin Resin), "EPPN-502H" (triphenol epoxy resin), "NC7000L" (naphthol novolac epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" manufactured by Nippon Kayaku Co., Ltd. (Biphenyl type epoxy resin), `` ESN475V '' (naphthol novolac type epoxy resin), `` ESN485 '' (naphthol novolac type epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., and `` YX4000H '' manufactured by Mitsubishi Chemical Corporation "," YL6121 "(biphenyl type epoxy resin)," YX4000HK "(bisxylenol type epoxy resin)," YX8800 "(anthracene type epoxy resin), and" PG "manufactured by Osaka Gas Chemical Co., Ltd. -100 "," CG-500 "," YL7800 "(芴 -type epoxy resin) manufactured by Mitsubishi Chemical Corporation," jER1010 "manufactured by Mitsubishi Chemical Corporation, (solid bisphenol A-type epoxy resin)," jER1031S " (Tetraphenylethane type epoxy resin), "YL7760" (bisphenol AF type epoxy resin), and the like.

As the liquid epoxy resin, it is preferable to have two or more epoxy groups in one molecule, and it is preferable to use a liquid aromatic epoxy resin at a temperature of 20 ° C. The solid epoxy resin has three or more molecules in one molecule. The epoxy group is preferably an aromatic epoxy resin which is solid at a temperature of 20 ° C. The term "aromatic epoxy resin" as used in the present invention means an epoxy resin having an aromatic ring structure in its molecule.

As the component (A), from the viewpoint of adjusting the contact angle X and the contact angle Y to a desired range, a fluorine-containing epoxy resin of a fluorine compound is preferred.

When liquid epoxy resin and solid epoxy resin are used as the epoxy resin, the content ratio of these (liquid epoxy resin: solid epoxy resin) ranges from 1: 0.1 to 1:15 depending on the mass ratio. Better. By setting the content ratio of the liquid epoxy resin to the solid epoxy resin within this range, it is possible to obtain i) moderate adhesion when used in the form of a resin sheet, and ii) used in the form of a resin sheet. It is possible to obtain sufficient flexibility, improve handleability, and iii) to obtain effects such as a cured product of a resin composition layer having sufficient breaking strength. From the viewpoint of the effects of i) to iii), the content ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) ranges from 1: 0.1 to the mass ratio. The range of 1:12 is more preferable, and the range of 1: 0.5 to 1:10 is even more preferable.

The content of the epoxy resin in the resin composition is preferably 5% by mass or more, more preferably 9% by mass or more, from the viewpoint of obtaining an excellent tensile fracture strength and an insulating layer showing insulation reliability. Preferably it is 13 mass% or more. The upper limit of the epoxy resin content is not particularly limited as long as the effects of the present invention can be exhibited, and is preferably 50% by mass or less, and more preferably 40% by mass or less.

In the present invention, the content of each component in the resin composition is a value when the nonvolatile component in the resin composition is 100% by mass unless otherwise specified.

When the resin composition of the present invention contains two or more (A) components, the mass when the non-volatile content in the resin composition of the fluorine-containing epoxy resin in the resin composition is 100% by mass is W _A , and the resin When the non-volatile content in the resin composition of the epoxy resin other than the fluorine-containing epoxy resin in the composition is 100% by mass, when the mass is W _B , W _B / W _A is preferably 1 to 10, and 1 to 5 For the better, 1 ~ 3 is even better.

The epoxy equivalent of the epoxy resin is preferably from 50 to 5000, more preferably from 50 to 3000, even more preferably from 80 to 2000, and even more preferably from 110 to 1,000. By setting it as this range, the bridge density of the hardened | cured material of a resin composition layer becomes sufficient, and an insulating layer with small surface roughness can be obtained. The epoxy equivalent can be measured in accordance with Japanese Industrial Standard JIS K7236, and is the mass of a resin containing 1 equivalent of an epoxy group.

The weight average molecular weight of the epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and even more preferably 400 to 1500. Here, the weight average molecular weight of the epoxy resin is a weight average molecular weight in terms of polystyrene measured by a gel permeation chromatography method (GPC) method.

<(B) Hardener>

The curing agent is not particularly limited as long as it has a function of curing an epoxy resin. Examples of the curing agent include a phenol-based hardener, a naphthol-based hardener, an active ester-based hardener, a benzoxazine-based hardener, and cyanide. Ester-based hardeners, carbodiimide-based hardeners, and the like. The hardener may be used alone or in combination of two or more.

As the phenol-based hardener and the naphthol-based hardener, from the viewpoints of heat resistance and water resistance, a phenol-based hardener having a phenolic structure or a naphthol-based hardener having a phenolic structure is preferred. From the standpoint of adhesion to the conductor layer, a nitrogen-containing phenol-based hardener is preferred, and a triazabenzene skeleton-containing phenol-based hardener is more preferred. Among them, a phenol novolac hardener containing a triazabenzene skeleton is preferred from the viewpoint of satisfying high heat resistance, water resistance, and adhesion to a conductor layer.

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

There are no particular restrictions on the active ester-based hardener, but it is generally preferred to use phenol esters, thiophenol esters, N-hydroxyamine esters, heterocyclic hydroxy compound esters, etc., having two in one molecule. The above-mentioned highly reactive ester-based compounds. The active ester-based hardener is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a hydrogenthio compound. Particularly from the viewpoint of improving heat resistance, an active ester-based hardener obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester-based hardener obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is hardened. The agent is better. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, methylene succinic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. . Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenol naphthalene, methylated bisphenol A, and methylated bisphenol F. , Methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1, 6-Dihydroxynaphthalene, 2,6-Dihydroxynaphthalene, Dihydroxybenzophenone, Trihydroxybenzophenone, Tetrahydroxybenzophenone, Resorcinol, Pyrogallol, Dicyclopentadiene Type Diphenol compounds, phenol novolacs, etc. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

Specifically, an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetic acid compound of phenol novolac, and an active ester compound containing a phenolic compound of phenol novolac Among them, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene type diphenol are more preferred. The "dicyclopentadiene-type diphenol structure" refers to a divalent structural unit composed of phenylene-cyclocyclodiene-phenylene.

Examples of commercially available active ester-based hardeners include active ester compounds containing a dicyclopentadiene-type diphenol structure, such as "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", and "HPC- "8000H-65TM" and "EXB-8000L-65TM" (manufactured by DIC). Examples of the active ester compound containing a naphthalene structure include "EXB9416-70BK" (manufactured by DIC), and an active ester compound containing an acetonide of phenol novolac. Examples include "DC808" (manufactured by Mitsubishi Chemical Corporation), and active ester compounds containing phenolic phenolic benzoate compounds include "YLH1026" (manufactured by Mitsubishi Chemical Corporation), and active ester-based hardeners containing acetic acid phenolic compounds. Examples thereof include "DC808" (manufactured by Mitsubishi Chemical Corporation), and examples of the active ester-based hardeners containing phenol phenolic benzoate include "YLH1026", "YLH1030", and "YLH1048" (manufactured by Mitsubishi Chemical Corporation).

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

Examples of the cyanate-based curing agent include bisphenol A dicyanate, polyphenol cyanate, oligosaccharides (3-methine-1,5-phenylene cyanate), 4,4 '-Methylenebis (2,6-dimethylphenylcyanate), 4,4'-ethylenediphenyldicyanate, hexafluorobisphenol A dicyanate, 2,2 -Bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5-dimethylphenyl) methane, 1 , 3-bis (4-cyanatephenyl-1- (methylethylene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) Polyfunctional cyanate resins such as ethers, polyfunctional cyanate resins induced by phenol novolac, cresol novolac, and the like, and some of these cyanate resins are prepolymers such as triazine. Specific examples of the cyanate-based curing agent include "PT30" and "PT60" (phenol-phenol-type polyfunctional cyanate resin) and "ULL-950S" (polyfunctional cyanate) manufactured by Lonza Japan. Ester resin), "BA230", "BA230S75" (a part or all of the bisphenol A dicyanate is triazetized into a prepolymer that becomes a triad), and the like.

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

The content ratio of epoxy resin and hardener is preferably in the range of 1: 0.01 to 1: 2 according to the ratio of [total number of epoxy groups of epoxy resin]: [total number of reactive groups of hardener], 1: 0.015 ~ 1: 1.5 is better, 1: 0.02 ~ 1: 1 is even better. Here, the reactive group of the hardener refers to an active hydroxyl group, an active ester group, and the like, and it varies depending on the type of the hardener. In addition, the total number of epoxy groups of an epoxy resin is a value obtained by dividing the mass of solid content of each epoxy resin by the epoxy equivalent with respect to the total amount of all epoxy resins. Is the value obtained by dividing the solid content of each hardener by the reactive group equivalent for the total of all hardeners. By making the content ratio of an epoxy resin and a hardener into such a range, the heat resistance of the hardened | cured material of a resin composition layer can be improved more.

In one embodiment, the resin composition includes the aforementioned epoxy resin and hardener. The resin composition is a mixture of a liquid epoxy resin and a solid epoxy resin each containing (A) as an epoxy resin (mass ratio of the liquid epoxy resin to the solid epoxy resin, preferably 1: 0.1 ~ 1: 15, more preferably 1: 0.3 ~ 1: 12, even more preferably 1: 0.6 ~ 1: 10), (B) as the hardener is selected from the group consisting of phenol-based hardener, naphthol-based hardener, and activity One or more of a group consisting of an ester-based hardener and a cyanate-based hardener (preferably one or more selected from the group consisting of an active ester-based hardener and a cyanate-based hardener).

The content of the hardener in the resin composition is not particularly limited, but is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less. The lower limit is not particularly limited, but it is preferably at least 2 mass%.

<(C) inorganic filler>

In one embodiment, the resin composition may contain an inorganic filler. The inorganic filler is not particularly limited, and examples thereof include silicon dioxide, aluminum oxide, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, and hydrotalcite ( Aluminum magnesium carbonate), boehmite (boehmite), aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, Strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconia, barium titanate, barium zirconate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and tungsten phosphate Acid zirconium and so on. Among these, silicon dioxide is particularly suitable. Examples of the silicon dioxide include amorphous silicon dioxide, fused silicon dioxide, crystalline silicon dioxide, synthetic silicon dioxide, and hollow silicon dioxide. In addition, spherical silica is preferred as the silica. The inorganic filler may be used singly or in combination of two or more kinds.

The average particle diameter of the inorganic filler is preferably 0.35 μm or less, more preferably 0.32 μm or less, even more preferably 0.3 μm or less, and still more preferably 0.29 μm or less. From the viewpoint of improving the dispersibility in the resin composition layer, the lower limit of the average particle diameter is preferably 0.05 μm or more, more preferably 0.06 μm or more, and still more preferably 0.07 μm or more. Examples of commercially available inorganic fillers having such an average particle diameter include "UFP-30" manufactured by Denki Kagaku Kogyo Co., Ltd. and "SPH516-05" manufactured by Nippon Steel & Sumikin Materials Co., Ltd. By adjusting the average particle diameter of the inorganic filler within the aforementioned range, insulation properties can be improved.

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

The inorganic filler is preferably surface-treated with a surface-treating agent. Examples of the surface treatment agent include (D) a fluorine-containing silane coupling agent described later, and surface treatment agents other than the component (D) (hereinafter also referred to as "other surface treatment agents"). The component (C) may also be surface-treated with the component (D), or may be surface-treated with another surface-treating agent. From the viewpoint of adjusting the contact angle X and the contact angle Y, the (C) component is performed by the (D) component. Surface treatment is better. The surface treatment agent may be used singly or in combination of two or more kinds.

As another surface treating agent, at least one type of surface treating agent other than a silane coupling agent, an alkoxysilane compound, and an organosiloxane compound other than (D) component is preferable. These can also be oligomers. Examples of other surface treatment agents include amine-based silane coupling agents, epoxy silane-based coupling agents, mercapto silane coupling agents, silane-based coupling agents, organic siloxane compounds, alkoxy silane compounds, and titanic acid. Salt-based coupling agents. Examples of commercially available surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd. and "KBM803" (3- Mercaptopropyltrimethoxysilane), "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KBM573" (N-phenyl-3-amine) manufactured by Shin-Etsu Chemical Industry Co., Ltd. Propyltrimethoxysilane), `` SZ-31 '' (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Industries, `` KBM103 '' (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industries, Shin-Etsu Chemical "KBM-4803" (long-chain epoxy-type silane coupling agent) manufactured by Kogyo Co., Ltd.

According to the degree of surface treatment of the surface treatment agent, from the viewpoint of improving the dispersibility of the inorganic filler, it is preferable to perform surface treatment with 0.2 to 2 parts by mass of the surface treatment agent for 100 parts by mass of the component (C). It is better to perform surface treatment with 0.2 parts by mass to 1 part by mass, and it is more preferable to perform surface treatment with 0.3 parts by mass to 0.8 part by mass.

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

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

From the viewpoint of improving the thickness stability of the resin composition layer, when the non-volatile content in the resin composition is 100% by mass, the content (filling amount) of the inorganic filler in the resin composition is preferably 50% by mass or more. It is more preferably 55 mass% or more, and still more preferably 60 mass% or more. The upper limit of the inorganic filler in the resin composition is preferably 85% by mass or less from the viewpoint of improving the film insulation properties and the tensile fracture strength of the insulating layer (hardened material of the resin composition layer). 80 mass% or less, more preferably 75 mass% or less.

<(D) fluorine-containing silane coupling agent>

In one embodiment, the resin composition of the present invention may contain a fluorine-containing silane coupling agent as a fluorine compound. By including a fluorine-containing silane coupling agent, the contact angle X and the contact angle Y can be adjusted.

Specific examples of the (D) component include "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. and the like. (D) A component may be used individually by 1 type, and may be used in combination of 2 or more type.

The aspect of the (D) component contained in the resin composition of the present invention is not particularly limited, and it is preferable that it is contained in the resin composition in the following forms (i) to (iii), and (i) or (ii) It is more preferable to contain it in a resin composition, and it is more preferable to contain it in a resin composition as (i). That is, it is preferable that the component (D) contains the surface treatment agent as the component (C) in the resin composition.

(i) (D) component contains the surface treating agent as (C) component.

(ii) (D) component is contained individually in a resin composition.

(iii) The component (D) contains a surface treatment agent as the component (C), and the component (D) is contained alone in the resin composition.

The term "(D) component contains a surface treatment agent as (C) component" means that (C) component is surface-treated with (D) component. In this case, the component (D) usually exists on the surface of the component (C). In addition, "the component (D) is contained alone in a resin composition" means that the component (D) does not contain the surface treating agent as a component (C). When the component (D) does not contain a surface treatment agent as the component (C), the component (C) is free from the resin composition.

The content of the component (D) is preferably 0.1% by mass or more, more preferably 0.15% by mass or more, and more preferably 0.2% by mass or more. The upper limit is not particularly limited, but it is preferably 5 mass% or less, more preferably 3 mass% or less, and even more preferably 1 mass% or less.

When the surface treatment agent containing the (D) component as the (C) component, from the viewpoint of improving the dispersibility of the inorganic filler according to the degree of surface treatment of the surface treatment agent, 100 parts by mass of the (C) component is 0.2 to 2 parts by mass of a surface treatment agent is preferably used for surface treatment, 0.2 to 1 part by mass is better for surface treatment, and 0.3 to 0.8 part by mass is more preferred for surface treatment.

<(E) thermoplastic resin>

In one embodiment, the resin composition of the present invention further contains (E) a thermoplastic resin.

Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyimide resin, and polyetherimide. The resin, polysulfone resin, polyether resin, polyphenylene ether resin, polycarbonate resin, polyether ether ketone resin, and polyester resin are preferably phenoxy resins. The thermoplastic resin may be used singly or in combination of two or more kinds.

The polystyrene equivalent weight average molecular weight of the thermoplastic resin is preferably in the range of 8,000 to 70,000, more preferably in the range of 10,000 to 60,000, and even more preferably in the range of 20,000 to 60,000. The polystyrene-equivalent weight average molecular weight of the thermoplastic resin is measured by a gel permeation chromatography (GPC) method. 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 manufactured by Showa Denko Corporation for the column. / K-804L, the mobile phase was measured using chloroform and the like at a column temperature of 40 ° C, and was calculated using a standard polystyrene calibration curve.

Examples of the phenoxy resin include those selected from a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a phenolic skeleton, a biphenyl skeleton, a fluorenone skeleton, and dicyclopentyl One or more types of phenoxy resins of a group consisting of a diene skeleton, a norbornene skeleton, a naphthalene skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton. . The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. A phenoxy resin may be used individually by 1 type, and may use 2 or more types together. Specific examples of the phenoxy resin include "1256" and "4250" (both phenoxy resin containing a bisphenol A skeleton) and "YX8100" (benzene containing a bisphenol S skeleton) manufactured by Mitsubishi Chemical Corporation Oxyresin) and "YX6954" (phenoxy resin containing bisphenol acetophenone skeleton), others include "FX280" and "FX293" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7482", etc.

Examples of the polyvinyl acetal resin include polyvinyl formal resin, polyvinyl butyral resin, and polyvinyl butyral resin. Specific examples of the polyvinyl acetal resin include, for example, "electrochemical butyral 4000-2", "electrochemical butyral 5000-A", and "electrochemical butyral" manufactured by Denka Kogyo Co., Ltd. 6000-C "," Electrobutyral 6000-EP ", S Lec BH series, BX series (e.g. BX-5Z), KS series (e.g. KS-1), BL series, BM series, etc. manufactured by Sekisui Chemical Industry Co., Ltd. .

Specific examples of the polyimide resin include "RICA COAT SN20" and "RICA COAT PN20" manufactured by Shin Nihon Chemical Co., Ltd. Specific examples of the polyfluorene imide resin include linear polyfluorene imide obtained by reacting a bifunctional hydroxyl-terminated polybutadiene, a diisocyanate compound, and a tetraprotic acid anhydride (Japanese Patent Application Laid-Open No. 2006-37083). Polyimide described in Japanese Laid-Open Patent Publication), polyimide containing polysiloxane skeleton (Polyimide described in Japanese Patent Laid-Open No. 2002-12667 and Japanese Patent Laid-Open No. 2000-319386, etc.)醯 imine.

Specific examples of the polyamidamine resin include "Vilomax HR11NN" and "Vilomax HR16NN" manufactured by Toyobo Corporation. Specific examples of the polyamidamine resin include denatured polyamidamines such as "KS9100" and "KS9300" (polyamidamines containing a polysiloxane skeleton) manufactured by Hitachi Chemical Industries, Ltd. Imidic acid.

Specific examples of the polyether fluorene resin include "PES5003P" manufactured by Sumitomo Chemical Corporation.

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

Among them, phenoxy resin and polyvinyl acetal resin are preferred as the thermoplastic resin. That is, in a suitable embodiment, the thermoplastic resin includes one or more selected from the group consisting of a phenoxy resin and a polyvinyl acetal resin.

When the resin composition contains a thermoplastic resin, the content of the thermoplastic resin is preferably 0.1% to 10% by mass, more preferably 0.2% to 5% by mass, and even more preferably 0.3% to 1% by mass.

<(F) Hardening accelerator>

In one embodiment, the resin composition of the present invention further contains (F) a hardening accelerator.

Examples of the hardening accelerator include a phosphorus-based hardening accelerator, an amine-based hardening accelerator, an imidazole-based hardening accelerator, a guanidine-based hardening accelerator, and a metal-based hardening accelerator. Amine-based hardening accelerators, imidazole-based hardening accelerators, and metal-based hardening accelerators are preferred, and amine-based hardening accelerators, imidazole-based hardening accelerators, and metal-based hardening accelerators are more preferred. A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the phosphorus-based hardening accelerator include triphenylphosphine, a phosphorus borate compound, tetraphenylphosphotetraphenylborate, n-butylphosphotetraphenylborate, tetrabutylphosphodecanoate, ( 4-methylphenyl) triphenylphosphothiothiocyanate, tetraphenylphosphothiothiocyanate, butyltriphenylphosphothiothiocyanate, etc., and triphenylphosphine, tetrabutylphosphodecanoate Better.

Examples of the amine-based hardening accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, and 2,4,6-tris (dimethyl) Aminomethyl) phenol, 1,8-diazabicyclo (5,4,0) -undecene, etc., with 4-dimethylaminopyridine, 1,8-diazabicyclo (5,4, 0) -undecene is preferred.

Examples of the imidazole-based hardening accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methylimidazole. , 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1 -Benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4 -Methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylbenzimidazole, 1-cyanoethyl-2-phenylbenzimidazole, 2 , 4-diamine-6- [2'-methylimidazole- (1 ')]-ethyl-s-triazabenzene, 2,4-diamine-6- [2'-undecylimidazole- (1 ')]-ethyl-s-triazabenzene, 2,4-diamine-6- [2'-ethyl-4'-methylimidazole- (1')]-ethyl-s- Triazabenzene, 2,4-diamine-6- [2'-methylimidazole- (1 ')]-ethyl-s-triazabenzene isocyanuric acid additive, 2-phenylimidazole Isotricyanic acid additive, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5hydroxymethylimidazole, 2,3-dihydroxy-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazole Onium, 2-methylimidazolium, 2-phenylimidazolium and other imidazole compounds and adducts of imidazole compounds and epoxy resins, while 2-ethyl-4-methylimidazole, 1-benzyl-2- Phenylimidazole is preferred.

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

Examples of the guanidine-based hardening accelerator include dicyandiamine, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, and 1- (o-tolyl group). ) Guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7- Methyl-1,5,7-triazabicyclo [4.4.0] dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1 -n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1 -Phenylbiguanide, 1- (o-tolyl) biguanide, and the like are preferably dicyandiamine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene.

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

When the nonvolatile content of the epoxy resin and the hardener is 100% by mass, the content of the hardening accelerator in the resin composition is not particularly limited, but it is preferably 0.01% to 3% by mass.

<(G) flame retardant>

In one embodiment, the resin composition of the present invention further contains (G) a flame retardant. Examples of the flame retardant include an organic phosphorus-based flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a polysiloxane flame retardant, and a metal hydroxide. The flame retardant can be used singly or in combination of two or more kinds.

As the flame retardant, a commercially available product can be used, and examples thereof include "" HCA-HQ "" manufactured by Sanko, and "PX-200" manufactured by Daiba Chemical Industries. As the flame retardant, it is preferred that it is not easily hydrolyzed. For example, 10- (2,5-dihydroxyphenyl) -10-hydrogen-9-oxo-10-phosphophenanthrene-10-oxide is preferred. .

When the resin composition contains a flame retardant, the content of the flame retardant is not particularly limited, and is preferably 0.5% by mass to 20% by mass, more preferably 0.5% by mass to 15% by mass, and 0.5% by mass to 10% by mass, and even more preferably .

<(H) Organic Filler>

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

As the rubber particles, commercially available products such as "EXL2655" manufactured by Dow Chemical Japan, "AC3401N" and "AC3816N" manufactured by Aika Industries, Ltd. can be used.

As the rubber particles, it is preferable to use, for example, "AC3816N" and "AC3401N" manufactured by Aika Industries, from the viewpoint of reducing the ionicity and lowering the water conductivity of the hardened product of the resin composition layer.

When the resin composition contains an organic filler, the content of the organic filler is preferably 0.1% to 20% by mass, more preferably 0.2% to 10% by mass, and even more preferably 0.3% to 5% by mass. Still more preferably, it is 0.5% to 3% by mass.

<(I) arbitrary additives>

In one embodiment, the resin composition of the present invention may further include other additives as necessary. Examples of such other additives include organometallic compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds, and additives. Resin additives such as adhesives, defoamers, leveling agents, adhesion-imparting agents, and coloring agents.

<Physical properties of resin composition>

When the resin composition of the present invention is cured at 100 ° C for 30 minutes and further cured at 180 ° C for 30 minutes to obtain a cured product, the contact angle of the surface of the cured product to water before the surface of the cured product is roughened. X (°), when the surface of the hardened surface is roughened, the contact angle with water is Y (°), XY ≦ 0 °, preferably XY ≦ -3 °, more preferably It is XY ≦ -5 °. The lower limit of X-Y is not particularly limited, and is preferably -50 ° or more, more preferably -40 ° or more, and more preferably -30 ° or more. When X-Y ≦ 0 °, the film insulation becomes good. X-Y can be measured in accordance with the method described in "Measurement of Contact Angle" described later.

When the resin composition of the present invention is cured at 100 ° C for 30 minutes, and further cured at 180 ° C for 30 minutes to obtain a cured product, the surface of the cured product is roughened, and the contact angle Y with respect to water is Y Is Y ≧ 80 °, preferably Y ≧ 83 °, and more preferably Y ≧ 85 °. The upper limit of the contact angle Y is not particularly limited, but is preferably 180 ° or less, more preferably 150 ° or less, and even more preferably 120 ° or less. With Y ≧ 80 °, the film insulation becomes good. The contact angle Y can be measured in accordance with the method described in <Measurement of Contact Angle> described later.

When the resin composition of the present invention is cured at 100 ° C for 30 minutes, and further cured at 180 ° C for 30 minutes to obtain a cured product, the contact angle X of the cured product surface to water before the surface of the cured product is roughened , Preferably X <80 °, more preferably X ≦ 79 °. The lower limit of the contact angle X is not particularly limited, but is preferably 30 ° or more, more preferably 40 ° or more, and more preferably 50 ° or more. By X <80 °, the film insulation becomes good. The contact angle X can be measured in accordance with the method described in <Measurement of Contact Angle> described later.

The procedure of the roughening process at the time of measuring a contact angle can be performed according to the method as described in <measurement of a contact angle> mentioned later. In detail, it is in a specific swelling liquid at 60 ° C for 5 minutes, followed by a specific oxidant solution at 80 ° C for 10 minutes, and finally immersed in a neutralization solution at 40 ° C for 5 minutes, and then dried at 80 ° C for 15 minutes.

[Resin sheet]

The resin sheet of the present invention includes a support and a resin composition layer provided on the support. The resin composition layer is formed of the resin composition of the present invention.

From the viewpoint of reducing the thickness of the printed wiring board, the thickness of the resin composition layer is preferably 15 μm or less, more preferably 12 μm or less, still more preferably 10 μm or less, and still more preferably 8 μm or less. Although the lower limit of the thickness of the resin composition is not particularly limited, it is usually 1 μm or more, 1.5 μm or more, 2 μm or more, and the like.

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

When a film made of a plastic material is used as a support, examples of the plastic material include polyethylene terephthalate (hereinafter also simply referred to as "PET"), polyethylene naphthalate ( Hereinafter also referred to as "PEN"), such as polyester, polycarbonate (hereinafter also referred to as "PC"), polymethyl methacrylate (hereinafter also referred to as "PMMA"), acrylic, cyclic polyolefin, triethylene Acetyl cellulose (TAC), polyether fluorene (PES), polyether ketone, polyimide and the like. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

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

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

Moreover, as a support body, the support body with a mold release layer which has a mold release layer on the surface joined to the resin composition layer can also be used. As a mold release agent used for the mold release layer of the support body with a mold release layer, for example, a group selected from the group consisting of an alkyd resin, a polyolefin resin, a urethane resin, and a silicone resin is mentioned. 1 or more release agents. A commercially available product may be used as a support with a release layer, for example, "SK-1" and "AL" manufactured by Lintec Corporation. PET film having a release layer containing a glycolic resin-based release agent as a main component. -5 "," AL-7 "," Lumirror T60 "manufactured by Toray," Purex "manufactured by Teijin, and" Unipeel "manufactured by UNITIKA.

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

The resin sheet can be produced by, for example, preparing a resin varnish in which the resin composition is dissolved in an organic solvent, applying the resin varnish to a support using a mold coater, or the like, and drying the resin composition 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, ethylene glycol ether acetate, propylene glycol methyl ether acetate, and diethylene glycol monoethyl Acetates such as ether acetate, diethylene glycol ethers such as ethylene glycol ether and diethylene glycol butyl ether, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamidine Ammonium solvents such as amines (DMAc) and N-methylrolidone. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

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

On the resin sheet, a protective film conforming to the support may be laminated on the surface (that is, the surface opposite to the support) not bonded to the support of the resin composition layer. The thickness of the protective film is not particularly limited, and is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to prevent dust mustard or the like from adhering to or damaging the surface of the resin composition layer. The resin sheet can be rolled into a roll shape and stored. When the resin sheet has a protective film, it can be used by removing the protective film.

The resin sheet of the present invention achieves an insulating layer (hardened product of a resin composition layer) excellent in film insulation. That is, the resin sheet of the present invention can be suitably used as a resin sheet for forming an insulating layer of a printed wiring board (for forming an insulating layer of a printed wiring board), and can be more suitably used as a resin for forming a printed wiring board. Resin sheet for an interlayer insulating layer (resin sheet for an interlayer insulating layer of a printed wiring board). In addition, for example, in a printed wiring board having a first conductor layer, a second conductor layer, and an insulating layer provided between the first conductor layer and the second conductor layer, the insulating layer can be formed by the resin sheet of the present invention, so that the first The thickness of the insulating layer between the first and second conductor layers is 6 μm or less (preferably 5.5 μm or less, and more preferably 5 μm or less), and it is excellent in insulation performance.

The insulating layer formed using the resin sheet (or resin composition) of the present invention exhibits good plating adhesion. That is, an insulating layer exhibiting good plating peel strength can be achieved. The peeling strength of the plating layer is preferably 1.5 kgf / cm or less, more preferably 1 kgf / cm or less, and even more preferably 0.8 kgf / cm or less. The upper limit should be 0.1 kgf / cm or more. The evaluation of the peeling strength of the plating layer can be measured according to a method described later (measurement of the plating adhesion (plating peeling strength)).

The insulating layer formed using the resin sheet (or resin composition) of the present invention showed good results in terms of insulation resistance after 200 hours under an environment of 130 ° C, 85RH%, and 3.3V. That is, an insulating layer showing a good insulation resistance value can be achieved. The upper limit of the insulation resistance value is preferably 10 ¹² Ω or less, more preferably 10 ¹¹ Ω or less, and even more preferably 10 ¹⁰ Ω or less. The lower limit is not particularly limited, but is preferably 10 ⁷ Ω or more, and more preferably 10 ⁸ Ω or more. The insulation resistance value can be measured in accordance with the method described in "Evaluation of Insulation Reliability of Insulation Layer" described later.

[Printed wiring board, manufacturing method of printed wiring board]

The printed wiring board of the present invention includes an insulating layer formed of a cured product of the resin composition of the present invention, a first conductor layer, and a second conductor layer. The insulating layer is provided between the first conductor layer and the second conductor layer, and insulates the first conductor layer from the second conductor layer (the conductor layer is also referred to as a wiring layer). Since the insulating layer formed by the cured product of the resin composition of the present invention is excellent in film insulation, it has excellent insulation even if the thickness of the insulating layer between the first and second conductor layers is 6 μm or less.

The thickness of the insulating layer between the first and second conductor layers is preferably 6 μm or less, more preferably 5.5 μm or less, and even more preferably 5 μm or less. The lower limit is not particularly limited, and may be 0.1 μm or more. The thickness of the insulating layer between the first and second conductor layers is, as an example shown in FIG. 1, the thickness t1 of the insulating layer 7 between the main surface 51 of the first conductor layer 5 and the main surface 61 of the second conductor layer 6. . The first and second conductor layers are conductor layers adjacent to each other with an insulating layer interposed therebetween, and the main surface 51 and the main surface 61 face each other. The thickness of the insulating layer between the first and second conductor layers can be measured according to the method described in <Measurement of Thickness of Insulating Layer Between Conductor Layers> described later.

The thickness t2 of the entire insulating layer is preferably 20 μm or less, more preferably 15 μm or less, and even more preferably 12 μm or less. The lower limit is not particularly limited, and may be 1 μm or more.

The printed wiring board of the present invention can be manufactured by a method including the following steps (I) and (II) using the aforementioned resin sheet.

(I) A step of laminating the inner layer substrate so that the resin composition layer of the resin sheet and the inner layer substrate are bonded to each other.

(II) A step of thermally curing the resin composition layer to form an insulating layer.

The "inner substrate" used in step (I) mainly refers to a substrate such as a glass polyester substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, or It is a circuit board in which a patterned conductor layer (circuit) is formed on one or both sides of the substrate. In addition, when a printed wiring board is manufactured, an inner-layer circuit board, which is an intermediate product to be formed with an insulating layer and / or a conductor layer, is also included in the "inner-layer substrate" referred to in the present invention. When the printed wiring board is a circuit board with built-in parts, an inner substrate having built-in parts must be used.

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

The lamination of the inner substrate and the resin sheet is preferably performed by a vacuum lamination method. In the vacuum lamination method, the heating and crimping temperature is preferably in the range of 60 ° C to 160 ° C, and more preferably in the range of 80 ° C to 140 ° C. The heating and crimping pressure is preferably 0.098MPa to 1.77MPa, and more preferably 0.29MPa to In the range of 1.47 MPa, 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. The lamination is preferably performed under a reduced pressure of a pressure of 26.7 hPa or less.

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

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

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

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

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

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

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

When manufacturing a printed wiring board, (III) a step of making holes in the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer may be further performed. These steps (III) to (V) can also be performed in accordance with various methods known to those skilled in the art for manufacturing printed wiring boards. When the support is removed after step (II), the support may be removed between step (II) and step (III), between step (III) and step (IV), and in step (IV). ) And step (V). In addition, if necessary, the formation of the insulating layer and the conductor layer of steps (II) to (V) is repeatedly performed to form a multilayer wiring board. In this case, the thickness (t1 in FIG. 1) of the insulating layer between the respective conductor layers is preferably within the aforementioned range.

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

Step (IV) is a step of roughening the insulating layer. The procedure and conditions of the roughening process are not particularly limited, and a known procedure and conditions generally used when forming an insulating layer of a printed wiring board can be adopted. For example, a swelling treatment by a swelling liquid, a roughening treatment by an oxidizing agent, and a neutralizing treatment by a neutralizing solution may be performed in order to sequentially roughen the insulating layer. The swelling liquid is not particularly limited, and examples thereof include an alkali solution and a surfactant solution, and an alkali solution is preferred. As the alkali solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferred. Examples of commercially available swelling liquids include Swelling Dip Securiganth P, Swelling Dip Securiganth SBU, etc. manufactured by Atotech Japan. The swelling treatment of the swelling liquid is not particularly limited. For example, the swelling liquid can be immersed in the swelling liquid at 30 ° C. to 90 ° C. for 1 to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to a moderate degree, it is preferable that the insulating layer is immersed in a swelling liquid at 40 ° C to 80 ° C for 5 to 15 minutes. The oxidant is not particularly limited, and examples thereof include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. According to the roughening treatment of an oxidant such as an alkaline permanganic acid solution, it is preferable to immerse the insulating layer for 10 to 30 minutes in an oxidant solution heated to 60 ° C to 80 ° C. In addition, the concentration of the permanganate in the alkaline permanganate solution is preferably 5% to 10% by mass. Examples of commercially available oxidants include alkaline permanganic acid solutions such as Concentrate Compact CP and Dosing Solution Securiganth P manufactured by Atotech Japan. The neutralizing solution is preferably an acidic aqueous solution, and examples of commercially available products include Reduction Solution Securiganth P manufactured by Atotech Japan. The treatment with the neutralizing solution can be performed by immersing the treated surface subjected to the roughening treatment with the oxidizing agent at 30 ° C to 80 ° C for 5 to 30 minutes. From the viewpoints of workability and the like, a method of immersing the object subjected to the roughening treatment with an oxidizing agent in a neutralizing solution at 40 ° C to 70 ° C for 5 to 20 minutes is preferable.

In an implementation form, the arithmetic average roughness Ra of the surface of the insulating layer after the roughening treatment is preferably 400 nm or less, more preferably 350 nm or less, and even more preferably 300 nm or less. The lower limit is not particularly limited, but is preferably 0.5 nm or more, and more preferably 1 nm or more. In addition, the root mean square roughness Rq of the surface of the insulating layer after the roughening treatment is preferably 400 nm or less, more preferably 350 nm or less, and even more preferably 300 nm or less. The lower limit is not particularly limited, and is preferably 0.5 nm or more, more preferably 1 nm or more. The arithmetic average roughness (Ra) and root mean square roughness (Rq) of the surface of the insulating layer can be measured using a non-contact surface roughness meter. The details can be described later (arithmetic average roughness (Ra), The measurement was performed according to the method described in Root Mean Square Roughness (Rq).

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

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

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

The thickness of the conductive layer varies depending on the design of the printed wiring board to be required, and is generally 3 μm to 35 μm, and preferably 5 μm to 30 μm.

In one embodiment, the conductor layer can also be formed by plating. For example, a conductive layer having a desired wiring pattern can be formed by plating on the surface of an insulating layer by a conventionally known technique such as a semi-active method and a power-active method. An example of forming a conductive layer by a semi-active method is shown below.

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

The resin sheet of the present invention can achieve a good insulation layer for part embedding, so it can be used appropriately even when the printed wiring board is a circuit board with built-in parts. The component-embedded circuit board can be manufactured by a conventional manufacturing method.

The printed wiring board manufactured using the resin sheet of the present invention may be an insulating layer including a hardened product of a resin composition layer of the resin sheet of the present invention, and an embedded wiring layer in which the insulating layer is embedded.

[Semiconductor device]

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

Examples of the semiconductor device include various semiconductor devices used in power supply gas products (for example, computers, mobile phones, digital cameras, and televisions) and vehicles (for example, motorcycles, automobiles, trams, ships, and airplanes).

The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor wafer) on a conductive space of a printed wiring board. The so-called "conducting place" is "a place for transmitting electrical signals to a printed wiring board", and the place may be a surface or a buried place. The semiconductor wafer is not particularly limited as long as it is a circuit element made of a semiconductor.

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

[Example]

Hereinafter, the present invention will be specifically described by way of examples. The invention is not limited to these examples. In addition, in the following, "part" and "%" mean "mass part" and "mass% (mass percentage)," respectively, unless otherwise specified.

<Measurement of average particle diameter of inorganic filler>

In a vial, 100 mg of an inorganic filler, 0.1 g of a dispersant ("SN9228" manufactured by Sannopco), and 10 g of methyl ethyl ketone were weighed out and dispersed by ultrasonic for 20 minutes. Using a laser diffraction type particle size distribution measuring device ("SALD-2200" manufactured by Shimadzu Corporation), the particle size distribution was measured in a fractional cell method, and the average particle diameter based on the median diameter was calculated.

<Measurement of Specific Surface Area of Inorganic Filler>

The specific surface area of the inorganic filler was measured using a BET full-automatic specific surface area measuring device (Macsorb HM-1210 manufactured by Moontech).

<Inorganic filler used>

Inorganic filler 1: 100 parts of spherical silicon dioxide ("SPH516-05" manufactured by Nippon Steel & Sumikin Materials Co., Ltd., with an average particle diameter of 0.29 μm and a specific surface area of 16.3 m ² / g), with 3,3,3- One part of trifluoropropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-7103) was surface-treated.

Inorganic filler 2: 100 parts of spherical silica ("SPH516-05" manufactured by Nippon Steel & Sumikin Materials Co., Ltd., with an average particle diameter of 0.29 μm and a specific surface area of 16.3 m ² / g), with N-phenyl-3 -One part of aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM573) was surface-treated.

Inorganic filler 3: 100 parts of spherical silica ("UFP-30" manufactured by Denka Kogyo Co., Ltd., with an average particle diameter of 0.078 μm and a specific surface area of 30.7 m ² / g), with 3,3,3-trifluoro Two parts of propyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-7103) were surface-treated.

Inorganic filler 4: 100 parts of spherical silica ("UFP-30" manufactured by Denka Kogyo Co., Ltd., with an average particle diameter of 0.078 μm and a specific surface area of 30.7 m ² / g), with N-phenyl-3-amine Two parts of propyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM573) were surface-treated.

Inorganic filler 5: For spherical silicon dioxide ("SC1500SQ"("SO-C1" with hexamethyldisilazane surface treatment) manufactured by Admatechs), the average particle diameter is 0.63 μm, and the specific surface area is 11.2 m ² / g 100 parts), and 1 part of N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd., KBM573) was surface-treated.

[Preparation of resin composition]

<Preparation of Resin Composition 1>

6 parts of bisxylenol epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185), naphthalene epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., epoxy equivalent 332) 10 parts, 10 parts of bisphenol AF epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent is about 238), 10 parts of bisphenol epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., Epoxy equivalent is about 169, 4 parts of bisphenol A type and bisphenol F type 1: 1 mixed product, phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation), cyclohexanone: methyl ethyl ketone with a solid content of 30% by mass (MEK) is a 1: 1 solution) 2 parts, and stirred in a mixed solvent of 20 parts of solvent naphtha and 10 parts of cyclohexanone, and heat-dissolved. After cooling to room temperature, 3 parts of a novolac-based hardener ("LA7054" manufactured by DIC Corporation, hydroxyl equivalent of about 125, 60% solids MEK solution) was mixed with this and the naphthol-based hardener was mixed. Agent ("SN-495V" manufactured by DIC Corporation, hydroxyl equivalent of about 231), 6 parts, 90 parts of inorganic filler 1, and 0.05 part of amine hardening accelerator (4-dimethylaminopyridine (DMAP)), based on After the high-speed rotating mixer was uniformly dispersed, it was filtered with a cassette filter ("SHP020" manufactured by ROKITECHNO) to prepare a resin composition 1.

<Preparation of Resin Composition 2>

6 parts of bisxylenol epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185), naphthalene epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., epoxy equivalent 332) 10 parts, 10 parts of bisphenol AF epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent is about 238), 10 parts of bisphenol epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., Epoxy equivalent is about 169, 4 parts of bisphenol A type and bisphenol F type 1: 1 mixed product, phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation), cyclohexanone: methyl ethyl ketone with a solid content of 30% by mass (MEK) is a 1: 1 solution) 2 parts, and stirred in a mixed solvent of 20 parts of solvent naphtha and 10 parts of cyclohexanone, and heat-dissolved. After cooling to room temperature, an o-methylphenol-based hardener containing a triazine skeleton ("LA3018-50P" manufactured by DIC Corporation) was mixed with 2-methoxypropane having a hydroxyl equivalent of about 151 and a solid content of 50%. Alcohol solution) 4 parts, active ester-based hardener ("EXB-8000L-65M" manufactured by DIC Corporation, active group equivalent about 220, non-volatile content 65% by mass MEK solution) 7 parts, 90 parts inorganic filler 2 With 0.05 part of amine hardening accelerator (4-dimethylaminopyridine (DMAP)), uniformly dispersed in a high-speed rotary mixer, and then filtered with a cartridge filter ("SHP020" manufactured by ROKITECHNO) to prepare Resin composition 2.

<Preparation of Resin Composition 3>

6 parts of bisxylenol epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185), naphthalene epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., epoxy equivalent 332) 20 parts, 2 parts of anisole type epoxy resin ("EXA-7311-G4" manufactured by DIC, epoxy equivalent about 213), 20 parts of solvent naphtha and cyclohexanone 10 parts of the mixed solvent was dissolved while heating. After cooling to room temperature, an o-methylphenol-based hardener containing a triazine skeleton ("LA3018-50P" manufactured by DIC Corporation) was mixed with 2-methoxypropane having a hydroxyl equivalent of about 151 and a solid content of 50%. Alcohol solution) 4 parts, active ester-based hardener ("EXB-8000L-65M" manufactured by DIC Corporation, active group equivalent about 220, non-volatile content 65% by mass MEK solution) 7 parts, 50 parts inorganic filler 3 And 0.05 parts of imidazole-based hardening accelerator (1B2PZ, 1-benzyl-2-phenylimidazole), uniformly dispersed with a high-speed rotary mixer, and filtered with a cartridge filter ("SHP020" manufactured by ROKITECHNO), A resin composition 3 was prepared.

<Preparation of Resin Composition 4>

6 parts of bisxylenol epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185), naphthalene epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., epoxy equivalent 332) 10 parts, 10 parts of bisphenol AF type epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 238), naphthalene ether type epoxy resin ("EXA-7311-G4" manufactured by DIC Corporation, The epoxy equivalent is about 213) 2 parts, and it is stirred in a mixed solvent of 20 parts of solvent naphtha and 10 parts of cyclohexanone, and it is heated and dissolved. After cooling to room temperature, an o-methylphenol-based hardener containing a triazine skeleton ("LA3018-50P" manufactured by DIC Corporation) was mixed with 2-methoxypropane having a hydroxyl equivalent of about 151 and a solid content of 50%. 4 parts of alcohol solution, 7 parts of active ester hardener ("EXB-8000L-65M" manufactured by DIC Corporation, active group equivalent of about 220, non-volatile content of 65% by mass MEK solution), 50 parts of inorganic filler 4 With 0.05 part of amine hardening accelerator (4-dimethylaminopyridine (DMAP)), uniformly dispersed in a high-speed rotary mixer, and then filtered with a cartridge filter ("SHP020" manufactured by ROKITECHNO) to prepare Resin composition 4.

<Preparation of Resin Composition 5>

6 parts of bisxylenol epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185), naphthalene epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., epoxy equivalent 332) 20 parts of cyclohexane epoxy resin ("ZX1658GS" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 135) 4 parts, stirred in a mixed solvent of 20 parts of solvent naphtha and 10 parts of cyclohexanone, Let it heat to dissolve. After cooling to room temperature, 3 parts of a novolac-based hardener ("LA7054" manufactured by DIC Corporation, hydroxyl equivalent of about 125, 60% solids MEK solution) was mixed with this and the naphthol-based hardener was mixed. Agent ("SN-495V" manufactured by DIC Corporation, hydroxyl equivalent of about 231), 6 parts, 80 parts of inorganic filler 5, and 0.05 part of amine hardening accelerator (4-dimethylaminopyridine (DMAP)). After the high-speed rotating mixer was uniformly dispersed, it was filtered with a cassette filter ("SHP020" manufactured by ROKITECHNO) to prepare a resin composition 5.

<Preparation of Resin Composition 6>

6 parts of bisxylenol epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185), naphthalene epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., epoxy equivalent 332) 20 parts, anisole type epoxy resin ("EXA-7311-G4" manufactured by DIC Corporation, epoxy equivalent of about 213), 2 parts, phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, solid content 30 parts by mass of 2 parts of cyclohexanone: methyl ethyl ketone (MEK) in a 1: 1 solution), and stirred in a mixed solvent of 20 parts of solvent naphtha and 10 parts of cyclohexanone, and dissolved by heating. After cooling to room temperature, an o-methylphenol-based hardener containing a triazine skeleton ("LA3018-50P" manufactured by DIC Corporation) was mixed with 2-methoxypropane having a hydroxyl equivalent of about 151 and a solid content of 50%. Alcohol solution) 4 parts, active ester-based hardener ("EXB-8000L-65M" manufactured by DIC Corporation, active group equivalent about 220, non-volatile content 65% by mass MEK solution) 7 parts, 80 parts inorganic filler 5 And 0.05 parts of imidazole-based hardening accelerator (1B2PZ, 1-benzyl-2-phenylimidazole), uniformly dispersed with a high-speed rotary mixer, and filtered with a cartridge filter ("SHP020" manufactured by ROKITECHNO), A resin composition 6 was prepared.

The ingredients used for the preparation of the resin compositions 1 to 6 and their blending amounts (parts by mass of non-volatile components) are shown in the following table. The abbreviations and the like in the following table are as follows.

YX4000HK: Dixylenol type epoxy resin, made by Mitsubishi Chemical Corporation, epoxy equivalent is about 185

ESN475V: Naphthalene type epoxy resin, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., epoxy equivalent is about 332

YL7760: Bisphenol AF epoxy resin, made by Mitsubishi Chemical Corporation, epoxy equivalent is about 238

EXA-7311-64: Naphthalene ether type epoxy resin, manufactured by DIC Corporation, epoxy equivalent is about 213

ZX1059: Bisphenol type epoxy resin, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., epoxy equivalent of 169, bisphenol A type and bisphenol F type 1: 1 mixed product

ZX1658GS: Cyclohexane epoxy resin, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent is about 135

LA3018-50P: o-methylphenol-based hardener containing a triazine skeleton, manufactured by DIC, with a hydroxyl equivalent of about 151 and a 2-methoxypropanol solution with a solid content of 50%

LA7054: Novolak-based hardener containing a triazine skeleton, manufactured by DIC Corporation, MEK solution with a hydroxyl equivalent of about 125 and a solid content of 60%

SN-495V: Naphthol-based hardener, manufactured by DIC Corporation, hydroxyl equivalent is about 231

EXB-8000L-65M: Active ester hardener, manufactured by DIC, MEK solution with an active group equivalent of about 220 and a non-volatile content of 65% by mass

YX7553BH30: phenoxy resin, manufactured by Mitsubishi Chemical Corporation, 30% by mass of cyclohexanone: methyl ethyl ketone (MEK) in 1: 1 solution

DMAP: amine hardening accelerator, 4-dimethylaminopyridine

1B2PZ: imidazole hardening accelerator, 1-benzyl-2-phenylimidazole

[Production of resin sheet]

As a support, a PET film ("Lumirror R80" manufactured by Toray Co., Ltd.) having a mold release treatment with an alkyd resin-based release agent ("AL-5" manufactured by LINTEC Corporation) was prepared. The thickness was 38 µm and the softening point was 130 ° C. "Release PET").

Each resin composition was uniformly coated with a mold coater so that the thickness of the dried resin composition layer became 13 μm on the release PET, and dried at 70 ° C. to 95 ° C. for 2 minutes, and then obtained on the release PET. Resin composition layer. Next, a rough surface of a polypropylene film ("ALPHAN MA-411" manufactured by Oji F-TEX Co., Ltd., thickness 15 µm) was used as a protective film on the surface of the resin sheet that was not joined to the support body to form a resin composition layer. The way of bonding is laminated. Thereby, a resin sheet composed of a release PET (support), a resin composition layer, and a protective film in this order was obtained.

[Evaluation test]

<Measurement of Roughness and Peeling Strength of Coating>

(Modulation of evaluation substrate)

(1) Bottom treatment of inner circuit board

As the inner-layer circuit board, a glass cloth substrate epoxy double-sided copper-clad laminated board (copper foil thickness of 3 μm) with a glass cloth substrate having a circuit conductor (copper) formed with a wiring pattern of L / S = 2 μm / 2 μm was prepared. The thickness of the substrate is 0.15mm. "HL832NSF LCA" manufactured by Mitsubishi Gas Chemical Co., Ltd. (size 255 × 340mm). Both sides of the inner-layer circuit board were treated with organic coating on the copper surface with "FlatBOND-FT" manufactured by MEC.

(2) Lamination of resin sheets

The protective film was peeled from each of the resin sheets produced in the examples and comparative examples, and a batch type vacuum pressure laminator (manufactured by Nikko-Materials, two-layer build-up laminator, CVP700) was used. The two-layer circuit board is connected to each other, and both sides of the inner-layer circuit board are laminated. The lamination was performed by depressurizing the air pressure for 30 seconds to 13 hPa or less, and crimping at 130 ° C and a pressure of 0.74 MPa for 45 seconds. Next, hot extrusion was performed at 120 ° C. and a pressure of 0.5 MPa for 75 seconds.

(3) Thermal curing of resin composition layer

The inner-layer circuit board on which the resin sheet was laminated was put into a furnace at 100 ° C for 30 minutes, and then moved to a furnace at 180 ° C for 30 minutes, and then heat-cured to form an insulating layer having a thickness of 5 m, and the release PET was peeled. This is referred to as "the evaluation substrate A".

(4) Steps for roughening

The evaluation substrate A on which the insulating layer was formed was subjected to a desmear process as a roughening process. In addition, as the desmearing treatment, the following wet desmearing treatment was performed.

Wet deslagging treatment:

Soak in a swelling liquid ("Swelling-dip sequricant P" produced by Atotech Japan, an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60 ° C for 5 minutes, and then in an oxidant solution (made by Atotech Japan) "Concentrate compact CP", an aqueous solution with a potassium permanganate concentration of about 6% and a sodium hydroxide concentration of about 4%, was immersed at 80 ° C for 10 minutes, and finally in a neutralizing solution ("Reduction solution sequricant" manufactured by Atotech Japan) P (transliteration), sulfuric acid aqueous solution) was immersed at 40 ° C for 5 minutes, and then dried at 80 ° C for 15 minutes.

(5) Steps for forming a conductor layer

(5-1) Electroless plating step

In order to form a conductor layer on the surface of the circuit board, a conductor plating step (copper plating step using a chemical solution manufactured by Atotech Japan) is performed including the following steps 1 to 6 to form a conductor layer.

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

The product name: Cleaning Cleaner Securiganth 902 (product name) was washed at 60 ° C for 5 minutes.

2. Soft etching (cleaning in through holes)

A sulfuric acid-acid sodium peroxodisulfate aqueous solution was used for 1 minute at 30 ° C.

3.Pre-dip (adjusting the charge on the surface of the insulating layer imparted to Pd)

Using Pre.Dip Neoganth B (trade name), it was treated at room temperature for 1 minute.

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

Using Activator Neoganth 834 (trade name), it was treated at 35 ° C for 5 minutes.

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

A mixed solution of Reducer Neoganth WA (trade name) and Reducer Acceralator 810 mod. (Trade name) was used and treated at 30 ° C for 5 minutes.

6. Non-electrolytic copper plating step (precipitate copper on the surface of the insulating layer (Pd surface))

A mixed solution of Basic Solution Printganth MSK-DK (trade name) and Copper solution Printganth MSK (trade name) and Stabilizer Printganth MSK-DK (trade name) and Reducer Cu (trade name) was used and treated at 35 ° C for 20 minutes. The thickness of the formed electroless copper-plated layer was 0.8 μm.

(5-2) Electrolytic plating step

Next, an electrolytic copper plating step was performed under the condition that copper was filled into the through holes using a chemical solution manufactured by Atotech Japan. Thereafter, as a resist pattern for patterning by etching, a land pattern with a diameter of 1 mm that is conducted to a through hole and a circular conductor pattern with a diameter of 10 mm that is not connected to a lower conductor are used in A conductor layer having a land and a conductor pattern was formed on the surface with a thickness of 10 μm. Next, annealing was performed at 200 ° C for 90 minutes. This substrate is referred to as "evaluation substrate B".

(Measurement of Arithmetic Mean Roughness (Ra) and Root Mean Square Roughness (Rq))

A non-contact surface roughness meter (WYKO NT3300 manufactured by Veeco Instruments) was used on the surface of the insulating layer other than the circular conductor pattern of the evaluation substrate B, and the measurement range was 121 μm in a VSI contact mode with a 50x lens. The value obtained by × 92 μm was used to determine the Ra value and Rq value. An average of 6 points was calculated, and the results of rounding to the next digit are shown in the table below.

(Measurement of Plating Adhesion (Plating Peel Strength))

For the conductive layer of the substrate B for evaluation, a part with a width of 10 mm and a length of 100 mm was introduced, and one end was peeled off and clamped by a grasping tool (manufactured by TSE, Autocom type inspection machine AC-50C-SL). The testing machine measured the load (kgf / cm) when pulling and peeling 35 mm in the vertical direction at a speed of 50 mm / min at room temperature, as the peel strength.

<Measurement of thickness of insulating layer between conductor layers>

The FIB-SEM composite apparatus ("SMI3050SE" manufactured by SII Nano Technology) was used to observe the cross section of the evaluation substrate B. For details, a vertical cross section was cut from the surface of the conductive layer by FIB (Beam Ion Beam), and the thickness of the insulating layer between the conductive layers was measured from the SEM image of the cross section. For each sample, cross-sectional SEM images of five randomly selected locations were observed, and the average value was shown in the following table as the thickness (μm) of the insulating layer between the conductor layers.

<Assessment of Insulation Reliability of Insulation Layer>

The 10 mm-diameter circular conductor side of the evaluation substrate B obtained above was used as a positive (+) electrode, and the grid-conductor (copper) side of the inner layer circuit substrate connected to the island with a diameter of 1 mm was a negative (-) electrode , Using a highly accelerated life test device ("PM422" manufactured by ETAC), the insulation resistance value at 200 hrs under conditions of 130 ° C, 85% relative humidity, and 3.3V DC voltage was applied as an electrochemical migration tester. ("ECM-100" manufactured by J-RAS) was measured. This measurement was performed 6 times. The value of the test piece was "○" when all resistance values were 10 ⁷ Ω or more, and "×" when the resistance value was less than 10 ⁷ Ω. The evaluation result and the insulation resistance value were evaluated. Shown in the table below. The insulation resistance values described in the following table are the lowest values of the insulation resistance values of the 6-point test pieces.

<Measurement of contact angle>

The contact angle of the surface of the hardened body by the droplet method of water droplets was measured using an automatic contact angle meter (DropMaster DMs-401 manufactured by Kyowa Interface Science Co., Ltd.). Specifically, a syringe was filled with pure water, and 1.0 μL of water droplets were prepared to adhere to the surface of the insulating layer of the substrate A for evaluation. The contact angle after 2000 ms with water droplets measured by the automatic contact angle meter was X (°).

Next, the roughening process of the insulating layer of the board | substrate A for evaluation was performed by the method similar to the process of roughening process (4) mentioned above. Then, a syringe was filled with pure water, and 1.0 μL of water droplets were produced to roughen the surface of the insulating layer adhered to the substrate A for evaluation. The contact angle after 2000 ms with water droplets was measured by the automatic contact angle meter, and was Y (°). When X-Y is 0 or less, it is "○", and when X-Y is more than 0, it is "×". In addition, "○" is indicated when Y is 80 ° or more, and "×" is indicated when it is less than 80 °.

Claims (14)

    A resin composition characterized by containing (A) an epoxy resin and (B) a hardener, and curing the resin composition at 100 ° C for 30 minutes and further at 180 ° C for 30 minutes to obtain a cured product, The contact angle of water on the surface of the hardened material before the roughening treatment is X (°), and the contact angle of water on the surface of the hardened material after roughening the hardened surface is Y (°) In this case, the relationship of XY ≦ 0 ° and Y ≧ 80 ° is satisfied.         For example, the resin composition according to the first patent application scope further contains (C) an inorganic filler.         For example, if the resin composition of the second item of the patent application is applied, when the non-volatile component in the resin composition is 100% by mass, the content of the (C) component is 50% by mass or more.         For example, the resin composition of the second or third item of the patent application range, wherein the average particle diameter of the component (C) is 0.05 μm to 0.35 μm.         For example, the resin composition of the scope of application for patent No. 1 contains a fluorine compound.         For example, the resin composition of the scope of application for patent No. 5 wherein the fluorine compound is a fluorine-containing epoxy resin.         For example, the resin composition of claim 5 in which the fluorine compound is (D) a fluorine-containing silane coupling agent.         For example, the resin composition according to item 7 of the patent application scope, wherein the (C) component is surface-treated by the (D) component.         For example, the resin composition of the scope of application for patent No. 1 is for forming an insulating layer of a printed wiring board.         A resin sheet is characterized in that it includes a support and a resin composition layer formed of the resin composition provided in any one of claims 1 to 9 of the scope of patent application provided on the support.         For example, the resin sheet of the scope of application for patent No. 10, wherein the thickness of the resin composition layer is 15 μm or less.         For example, the thin resin sheet of the scope of patent application No. 11 is a printed wiring board including a first conductor layer, a second conductor layer, and an insulation layer having a thickness of 6 μm or less formed between the first conductor layer and the second conductor layer. For the formation of this insulating layer.         A printed wiring board, comprising a printed wiring board including a first conductor layer, a second conductor layer, and an insulating layer having a thickness of 6 μm or less formed between the first conductor layer and the second conductor layer. The insulating layer is The hardened product of the resin composition of any one of the scope of application for patents 1 to 9.         A semiconductor device is characterized in that it includes a printed wiring board according to item 13 of the scope of patent application.