JP2018021106A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition which can impart a thin insulating layer excellent in insulating performance; a resin sheet containing the resin composition; a printed wiring board having a thin insulating layer excellent in insulating performance; and a semiconductor device.SOLUTION: A resin composition contains (A) an epoxy resin and (B) a curing agent, where when a cured product is obtained by thermally curing the resin composition at 100°C for 30 minutes and at 180°C for 30 minutes, a contact angle of the surface of the cured product before subjected to roughening treatment to water is represented by X (°) and a contact angle of the surface of the cured product after subjected to roughening treatment to water is represented by Y (°), relationships of X-Y≤0° and Y≥80° hold.SELECTED DRAWING: None

Description

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

  In recent years, in order to achieve miniaturization of electronic devices, the printed wiring board has been further reduced in thickness, and the thickness of the inner layer substrate and the insulating layer tends to be further reduced. As a material for reducing the thickness of an inner layer substrate or an insulating layer, for example, a thin film resin composition described in Patent Document 1 is known.

JP 2014-152309 A

  In Patent Document 1, the present inventors have found that when a thin film is applied to an insulating layer, the roughness tends to increase and the peel strength tends to decrease, and in order to solve these problems It has been proposed that the blending amount of the thermoplastic resin is a predetermined amount. However, in this document, no consideration is given to the insulation performance (hereinafter also referred to as “thin film insulation”) when the thickness of the insulating layer is reduced.

  When the insulating layer is a thin film, the inorganic filler particles come into contact with each other and the current easily flows through the interface, or the capacitance of the insulating layer is increased and the short circuit is likely to occur. For example, it becomes difficult to maintain the insulation performance as compared with the conventional one.

  An object of the present invention is to provide a resin composition capable of providing a thin insulating layer excellent in insulating performance; a resin sheet containing the resin composition; a printed wiring board including a thin insulating layer excellent in insulating performance; and a semiconductor device It is to provide.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the contact angle of the cured product surface with water before the roughening treatment of the resin composition and the roughening treatment of the cured product of the resin composition It was found that by making the contact angle of water on the surface of the cured product with water within a specific range, the thin film insulation was improved, and the present invention was completed.

That is, the present invention includes the following contents.
[1] A resin composition containing (A) an epoxy resin and (B) a curing agent,
When a cured product was obtained by thermosetting the resin composition at 100 ° C. for 30 minutes and further at 180 ° C. for 30 minutes, the contact angle of the cured product surface with water before roughening the surface of the cured product was X (° ), And when the contact angle of water on the surface of the cured product after roughening the surface of the cured product is Y (°),
A resin composition satisfying the relationship of XY ≦ 0 ° and Y ≧ 80 °.
[2] The resin composition according to [1], further comprising (C) an inorganic filler.
[3] The resin composition according to [2], wherein the content of the component (C) is 50% by mass or more when the nonvolatile component in the resin composition is 100% by mass.
[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], which contains a fluorine compound.
[6] The resin composition according to [5], wherein the fluorine compound is a fluorine-containing epoxy resin.
[7] The resin composition according to [5] or [6], wherein the fluorine compound is (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], which is for forming an insulating layer of a printed wiring board.
[10] A resin sheet comprising a support and a resin composition layer formed on the support and formed from the resin composition according to any one of [1] to [9].
[11] The resin sheet according to [10], wherein the resin composition layer has a thickness of 15 μm or less.
[12] 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 resin sheet according to [11], which is used for forming the insulating layer.
[13] 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. And
The insulating layer is a printed wiring board which is a cured product of the resin composition according to any one of [1] to [9].
[14] A semiconductor device including the printed wiring board according to [13].

  According to the present invention, a resin composition capable of providing a thin insulating layer excellent in insulating performance; a resin sheet containing the resin composition; a printed wiring board including a thin insulating layer excellent in insulating performance; and a semiconductor device Can be provided.

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

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

[Resin composition]
The resin composition of the present invention is a resin composition containing (A) an epoxy resin and (B) a curing agent, and the resin composition is thermally cured at 100 ° C. for 30 minutes and further at 180 ° C. for 30 minutes. When the cured product is obtained, the contact angle of the cured product surface with water before roughening the cured product surface is set to X (°), and the cured product surface is subjected to the roughened treatment with respect to water on the cured product surface. When the contact angle is Y (°), the relationship of XY ≦ 0 ° and Y ≧ 80 ° is satisfied. By adjusting the contact angle X and the contact angle Y so that the relationship of X−Y ≦ 0 ° and Y ≧ 80 ° is satisfied, the surface of the insulating layer is hydrophobized, so that moisture penetrates into the insulating layer. This makes it possible to provide a thin insulating layer with excellent insulating performance. Hereinafter, when the resin composition is thermally cured at 100 ° C. for 30 minutes and further at 180 ° C. for 30 minutes to obtain a cured product, the contact angle with respect to water of the cured product surface before the roughening treatment is referred to as “contact angle X”. In some cases, when the cured product is obtained by thermosetting the resin composition at 100 ° C. for 30 minutes and further at 180 ° C. for 30 minutes, the contact angle with water on the surface of the cured product after the roughening treatment is expressed as “contact”. Sometimes referred to as “angle Y”.
Here, the contact angle refers to an angle formed by the liquid surface and the solid surface (takes an angle inside the liquid) where the free surface of the stationary liquid is in contact with the solid wall.

  If necessary, the resin composition may further comprise (C) an inorganic filler, (D) a fluorine-containing silane coupling agent, (E) a thermoplastic resin, (F) a curing accelerator, (G) a flame retardant, and (H ) It may contain additives such as organic fillers. Moreover, it is preferable that the resin composition of this invention contains a fluorine compound from a viewpoint of adjusting the contact angle X and the contact angle Y to a desired range. A 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. Moreover, the weight average molecular weight of a fluorine compound is 100-5000 normally. The fluorine compound is preferably contained as any one of the components (A) to (H), and the fluorine compound is preferably contained as the component (A) and / or contained as the component (D). A fluorine compound may be used individually by 1 type, and may be used in combination of 2 or more type. Moreover, when a fluorine compound contains as (A) component, you may use (A) component combining (A) component which is not a fluorine compound and a fluorine compound. Hereinafter, each component contained in the resin composition of the present invention will be described in detail.

<(A) Epoxy resin>
(A) Examples of the epoxy resin include fluorine-containing epoxy resins such as bisphenol AF type epoxy resins and perfluoroalkyl type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, dicyclo Pentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type Epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, butadiene structure Epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, etc. Can be mentioned. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type.

  The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. When the nonvolatile component of the epoxy resin is 100% by mass, at least 50% by mass or more is preferably an epoxy resin having two or more epoxy groups in one molecule. Among them, it has two or more epoxy groups in one molecule, and has a liquid epoxy resin (hereinafter referred to as “liquid epoxy resin”) at a temperature of 20 ° C. and three or more epoxy groups in one molecule, It is preferable to contain a solid epoxy resin (hereinafter referred to as “solid epoxy resin”) at a temperature of 20 ° C. By using a liquid epoxy resin and a solid epoxy resin in combination as the epoxy resin, the epoxy resin has excellent flexibility and the breaking strength of the cured product is improved.

  Liquid epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, and ester skeletons. Preferred are cycloaliphatic epoxy resins, cyclohexanedimethanol type epoxy resins, glycidylamine type epoxy resins, and epoxy resins having a butadiene structure. Glycidylamine type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, 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” (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation. "JER807" (bisphenol F type epoxy resin), "jER152" (phenol novolak type epoxy resin), "YL7760" (bisphenol AF type epoxy resin), "630", "630LSD" (glycidylamine type epoxy resin), Nippon Steel “ZX1059” (mixed product of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Sumikin Chemical Co., Ltd., “YD-8125G” (bisphenol A type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., “ EX-7 1 "(glycidyl ester type epoxy resin)," Celoxide 2021P "(alicyclic epoxy resin having an ester skeleton) manufactured by Daicel," PB-3600 "(epoxy resin having a butadiene structure), manufactured by Nippon Steel Chemical Co., Ltd. "ZX1658", "ZX1658GS" (liquid 1,4-glycidylcyclohexane), "630LSD" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "E-7432", "E-7632" manufactured by Daikin Industries, Ltd. (Perfluoroalkyl type epoxy resin) and the like. These may be used alone or in combination of two or more.

  Solid epoxy resins include naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, Anthracene type epoxy resin, bisphenol A type epoxy resin, and tetraphenylethane type epoxy resin are preferable, and naphthalene type tetrafunctional 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 tetrafunctional epoxy resin), “N-690” (manufactured by DIC) Cresol novolac type epoxy resin), "N-695" (cresol 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 ”(naphthylene ether type epoxy resin),“ EPPN-502H ”(manufactured by Nippon Kayaku Co., Ltd.) Trisphenol type epoxy resin), "NC7000L" (naphthol novolac type epoxy) Fat), “NC3000H”, “NC3000”, “NC3000L”, “NC3100” (biphenyl type epoxy resin), “ESN475V” (naphthalene type epoxy resin), “ESN485” (naphthol novolak type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. ), “YX4000H”, “YL6121” (biphenyl type epoxy resin), “YX4000HK” (bixylenol type epoxy resin), “YX8800” (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation, “PG” manufactured by Osaka Gas Chemical Co., Ltd. -100 "," CG-500 "," YL7800 "(fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation," jER1010 "manufactured by Mitsubishi Chemical Corporation (solid bisphenol A type epoxy resin)," jER1031S "(tetraphenyl) Ethane type epoxy tree ), And the like.

  The liquid epoxy resin is preferably an aromatic epoxy resin having two or more epoxy groups in one molecule and a liquid at a temperature of 20 ° C. The solid epoxy resin has three or more epoxy groups in one molecule. And an aromatic epoxy resin that is solid at a temperature of 20 ° C. is preferable. In addition, the aromatic epoxy resin as used in the field of this invention means the epoxy resin which has an aromatic ring structure in the molecule | numerator.

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

  When a liquid epoxy resin and a solid epoxy resin are used in combination as an epoxy resin, the quantitative ratio thereof (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.1 to 1:15 in terms of mass ratio. preferable. By making the quantity ratio of the liquid epoxy resin and the solid epoxy resin within such a range, i) suitable adhesiveness is obtained when used in the form of a resin sheet, ii) when used in the form of a resin sheet Sufficient flexibility is obtained, handling properties are improved, and iii) a cured product of the resin composition layer having sufficient breaking strength can be obtained. From the viewpoint of the effects i) to iii), the quantitative ratio of liquid epoxy resin to solid epoxy resin (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.1 to 1:12 in terms of mass ratio. 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, and still more preferably 13% by mass from the viewpoint of obtaining an insulating layer exhibiting good tensile fracture strength and insulation reliability. % Or more. Although the upper limit of content of an epoxy resin is not specifically limited as long as the effect of this invention is show | played, Preferably it is 50 mass% or less, More preferably, it is 40 mass% or less.

  In addition, in this invention, content of each component in a resin composition is a value when the non-volatile component in a resin composition is 100 mass% unless there is separate description.

The resin composition of the present invention, if it contains two or more component (A), the mass when the non-volatile components of the fluorine-containing epoxy resin in the resin composition in the resin composition is 100 mass% W _A, when the mass when the non-volatile components of the fluorine-containing epoxy resin other than the epoxy resin resin composition of the resin composition was 100% by mass was W _B, W _{B /} W _a has from 1 to 10 Preferably, it is 1-5, more preferably 1-3.

  The epoxy equivalent of the epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, and even more preferably 110 to 1000. By being in this range, the crosslinked density of the cured product of the resin composition layer is sufficient, and an insulating layer having a small surface roughness can be provided. The epoxy equivalent can be measured according to JIS K7236, and is the mass of a resin containing 1 equivalent of an epoxy group.

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

<(B) Curing agent>
The curing agent is not particularly limited as long as it has a function of curing an epoxy resin. For example, a phenolic curing agent, a naphthol curing agent, an active ester curing agent, a benzoxazine curing agent, a cyanate ester Examples thereof include a curing agent and a carbodiimide curing agent. A hardening | curing agent may be used individually by 1 type, or may use 2 or more types together.

  As the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable from the viewpoint of heat resistance and water resistance. Moreover, from a viewpoint of adhesiveness with a conductor layer, a nitrogen-containing phenol type hardening | curing agent is preferable and a triazine frame | skeleton containing phenol type hardening | curing agent is more preferable. Among these, a triazine skeleton-containing phenol novolac curing agent is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion to the conductor layer.

  Specific examples of the phenol-based curing agent and the naphthol-based curing agent include, for example, “MEH-7700”, “MEH-7810”, “MEH-7785” manufactured by Meiwa Kasei Co., Ltd., “NHN” manufactured by Nippon Kayaku Co., Ltd. “CBN”, “GPH”, “SN170”, “SN180”, “SN190”, “SN475”, “SN485”, “SN495”, “SN-495V”, “SN375”, “SN395” manufactured by Nippon Steel & Sumikin Co., Ltd. “TD-2090”, “LA-7052”, “LA-7054”, “LA-1356”, “LA-3018-50P”, “EXB-9500” and the like manufactured by DIC.

  Although there is no restriction | limiting in particular as an active ester type hardening | curing agent, Generally 1 molecule of ester groups with high reaction activity, such as phenol ester, thiophenol ester, N-hydroxyamine ester, ester of a heterocyclic hydroxy compound, are carried out. A compound having two or more thereof is preferably used. The active ester curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, Benzenetriol, dicyclopentadiene type diphenol compound, phenol novolac and the like can be mentioned. Here, the “dicyclopentadiene type diphenol compound” refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

  Specifically, an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of a phenol novolac, and an active ester compound containing a benzoylated product of a phenol novolac are preferred, Of these, active ester compounds having a naphthalene structure and active ester compounds having a dicyclopentadiene type diphenol structure are more preferred. The “dicyclopentadiene type diphenol structure” represents a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

  Commercially available active ester curing agents include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H-" as active ester compounds containing a dicyclopentadiene type diphenol structure. 65TM "," EXB-8000L-65TM "(manufactured by DIC)," EXB9416-70BK "(manufactured by DIC) as an active ester compound containing a naphthalene structure, and" DC808 "as an active ester compound containing an acetylated product of phenol novolac ( Mitsubishi Chemical Co., Ltd.), “YLH1026” (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing a benzoylated product of phenol novolac, “DC808” (manufactured by Mitsubishi Chemical Corporation) as an active ester curing agent which is an acetylated product of phenol novolac, "YLH1026" as an active ester-based curing agent is benzoyl product of E Nord novolac (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation), and the like.

  Specific examples of the benzoxazine-based curing agent include “HFB2006M” manufactured by Showa Polymer Co., Ltd. and “Pd” and “Fa” manufactured by Shikoku Kasei Kogyo Co., Ltd.

  Examples of the cyanate ester curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 4,4. '-Ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5-dimethyl) Bifunctional cyanate resins such as phenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether, phenol Novolac and K Polyfunctional cyanate resin derived from tetrazole novolac, these cyanate resins and partially triazine of prepolymer. Specific examples of the cyanate ester curing agent include “PT30” and “PT60” (phenol novolac type polyfunctional cyanate ester resin), “ULL-950S” (polyfunctional cyanate ester resin), and “BA230” manufactured by Lonza Japan. , “BA230S75” (a prepolymer in which part or all of bisphenol A dicyanate is triazine-modified into a trimer), and the like.

  Specific examples of the carbodiimide curing agent include “V-03” and “V-07” manufactured by Nisshinbo Chemical Co., Ltd.

  The amount ratio of the epoxy resin and the curing agent is preferably a ratio of [total number of epoxy groups of the epoxy resin]: [total number of reactive groups of the curing agent] in the range of 1: 0.01 to 1: 2. 1: 0.015 to 1: 1.5 are more preferable, and 1: 0.02 to 1: 1 are more preferable. Here, the reactive group of the curing agent is an active hydroxyl group, an active ester group or the like, and varies depending on the type of the curing agent. Moreover, the total number of epoxy groups of the epoxy resin is a value obtained by dividing the value obtained by dividing the solid mass of each epoxy resin by the epoxy equivalent for all epoxy resins, and the total number of reactive groups of the curing agent is: The value obtained by dividing the solid mass of each curing agent by the reactive group equivalent is the total value for all curing agents. By making the quantity ratio of an epoxy resin and a hardening | curing agent into such a range, the heat resistance of the hardened | cured material of a resin composition layer improves more.

  In one embodiment, the resin composition includes the aforementioned epoxy resin and a curing agent. The resin composition is a mixture of a liquid epoxy resin and a solid epoxy resin (A) as an epoxy resin (mass ratio of liquid epoxy resin: solid epoxy resin is preferably 1: 0.1 to 1:15, more preferably 1: 0.3-1: 12, more preferably 1: 0.6-1: 10), (B) a phenolic curing agent, a naphthol curing agent, an active ester curing agent and a cyanate ester One or more selected from the group consisting of curing agents (preferably one or more selected from the group consisting of active ester curing agents and cyanate ester curing agents) are preferably included.

  Although content of the hardening | curing agent in a resin composition is not specifically limited, Preferably it is 30 mass% or less, More preferably, it is 25 mass% or less, More preferably, it is 20 mass% or less. The lower limit is not particularly limited but is preferably 2% by mass or more.

<(C) Inorganic filler>
In one embodiment, the resin composition may contain an inorganic filler. The material of the inorganic filler is not particularly limited. For example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, water Aluminum oxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide , Zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Of these, silica is particularly preferred. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Moreover, spherical silica is preferable as the silica. An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type.

  The average particle size of the inorganic filler is preferably 0.35 μm or less, more preferably 0.32 μm or less, further preferably 0.3 μm or less, and even more preferably 0.29 μm or less. From the viewpoint of improving 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 further 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. Insulating properties can be improved by adjusting the average particle size of the inorganic filler within the above range.

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

  The inorganic filler is preferably surface-treated with a surface treatment agent. Examples of the surface treatment agent include (D) a fluorine-containing silane coupling agent, which will be described later, and a surface treatment agent other than the component (D) (hereinafter also referred to as “other surface treatment agent”). The component (C) may be surface-treated with the component (D) or may be surface-treated with another surface treatment agent. From the viewpoint of adjusting the contact angle X and the contact angle Y, the component (C) Is preferably surface-treated with component (D). A surface treating agent may be used individually by 1 type, and may be used in combination of 2 or more types.

  As the other surface treatment agent, at least one kind of surface treatment agent of a silane coupling agent other than the component (D), an alkoxysilane compound, and an organosilazane compound is preferable. These may be oligomers. Examples of other surface treatment agents include aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, organosilazane compounds, titanate coupling agents, and the like. Examples of commercially available surface treatment agents include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM803” (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu. “KBE903” (3-aminopropyltriethoxysilane) manufactured by Chemical Industry Co., Ltd. “KBM573” (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “SZ-31” manufactured by Shin-Etsu Chemical Co., Ltd. ( Hexamethyldisilazane), “KBM103” (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM-4803” (long-chain epoxy type silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

  The degree of the surface treatment with the surface treatment agent is 0.2 to 2 parts by mass of the surface treatment agent with respect to 100 parts by mass of component (C) from the viewpoint of improving the dispersibility of the inorganic filler. The surface treatment is preferably performed at 0.2 parts by mass to 1 part by mass, and preferably at 0.3 parts by mass to 0.8 parts by mass.

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

  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 as a solvent is added to the inorganic filler surface-treated with the surface treatment agent and ultrasonically cleaned at 25 ° C. for 5 minutes. After removing the supernatant and drying the solid, the carbon amount per unit surface area of the inorganic filler can be measured using a carbon analyzer. 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, the content (filling amount) of the inorganic filler in the resin composition is preferably 50 masses when the nonvolatile component in the resin composition is 100 mass%. % Or more, more preferably 55% by mass or more, and still more preferably 60% by mass or more. The upper limit of the content of the inorganic filler in the resin composition is preferably 85% by mass or less, more preferably from the viewpoint of improvement in thin film insulation and tensile fracture strength of the insulating layer (cured product of the resin composition layer). Is 80% by mass or less, more preferably 75% by 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. The contact angle X and the contact angle Y can be adjusted by containing a fluorine-containing silane coupling agent.

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

Although the aspect of (D) component contained in the resin composition of this invention is not specifically limited, It is preferable to contain in the resin composition in the aspect of the following (i)-(iii), (i) or (ii) ) Is more preferably contained in the resin composition, and more preferably in the resin composition in the form (i). That is, the component (D) is preferably contained in the resin composition as a surface treatment agent for the component (C).
(I) (D) component contains as a surface treating agent of (C) component.
(Ii) Component (D) contained alone in the resin composition.
(Iii) The component (D) is contained as a surface treatment agent for the component (C), and the component (D) alone is contained in the resin composition.
“Contained as component (D) as a surface treatment agent for component (C)” means that component (C) is surface-treated with component (D). In this case, the component (D) is usually on the surface of the component (C). Moreover, “(D) component alone contained in resin composition” means that (D) component is not contained as a surface treatment agent for (C) component. In addition, when (D) component does not contain as a surface treating agent of (C) component, (C) component is free in 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 further preferably 0.2% by mass or more. Although an upper limit is not specifically limited, 5 mass% or less is preferable, 3 mass% or less is more preferable, and 1 mass% or less is further more preferable.

  When component (D) is included as the surface treatment agent for component (C), the degree of surface treatment with the surface treatment agent is based on 100 parts by weight of component (C) from the viewpoint of improving dispersibility of the inorganic filler. Surface treatment is preferably performed with 0.2 to 2 parts by mass of a surface treatment agent, preferably 0.2 to 1 part by mass, and preferably 0.3 to 0. It is preferable that the surface treatment is performed at 8 parts by mass.

<(E) Thermoplastic resin>
In one embodiment, the resin composition of the present invention may further contain (E) a thermoplastic resin.

  Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, and polyether. Examples include ether ketone resins and polyester resins, and phenoxy resins are preferred. A thermoplastic resin may be used individually by 1 type, or may be used in combination of 2 or more type.

  The weight average molecular weight in terms of polystyrene 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 still more preferably in the range of 20,000 to 60,000. The weight average molecular weight in terms of polystyrene of the thermoplastic resin is measured by a gel permeation chromatography (GPC) method. Specifically, the polystyrene-converted weight average molecular weight of the thermoplastic resin is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K-804L / K- manufactured by Showa Denko KK as a column. 804L can be calculated using a standard polystyrene calibration curve by measuring the column temperature at 40 ° C. using chloroform or the like as the mobile phase.

  Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene Examples thereof include phenoxy resins having a skeleton and one or more skeletons selected from the group consisting of 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 be used in combination of 2 or more type. Specific examples of the phenoxy resin include “1256” and “4250” (both bisphenol A skeleton-containing phenoxy resin), “YX8100” (bisphenol S skeleton-containing phenoxy resin), and “YX6954” (bisphenolacetophenone) manufactured by Mitsubishi Chemical Corporation. In addition, “FX280” and “FX293” manufactured by NS ”,“ YL7213 ”,“ YL7290 ”,“ YL7482 ”, and the like.

  Examples of the polyvinyl acetal resin include a polyvinyl formal resin and a polyvinyl butyral resin, and a polyvinyl butyral resin is preferable. Specific examples of the polyvinyl acetal resin include, for example, “Electrical butyral 4000-2”, “Electrical butyral 5000-A”, “Electrical butyral 6000-C”, “Electrical butyral 6000-EP”, and Sekisui. Examples include ESREC BH series, BX series (for example, BX-5Z), KS series (for example, KS-1), BL series, and BM series manufactured by Chemical Industries.

  Specific examples of the polyimide resin include “Rika Coat SN20” and “Rika Coat PN20” manufactured by Shin Nippon Rika Co., Ltd. Specific examples of the polyimide resin include linear polyimide obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (polyimide described in JP-A-2006-37083), a polysiloxane skeleton. Examples thereof include modified polyimides such as containing polyimide (polyimides described in JP-A Nos. 2002-12667 and 2000-319386).

  Specific examples of the polyamideimide resin include “Vilomax HR11NN” and “Vilomax HR16NN” manufactured by Toyobo Co., Ltd. Specific examples of the polyamide-imide resin also include modified polyamide-imides such as “KS9100” and “KS9300” (polysiloxane skeleton-containing polyamideimide) manufactured by Hitachi Chemical Co., Ltd.

  Specific examples of the polyethersulfone resin include “PES5003P” manufactured by Sumitomo Chemical Co., Ltd.

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

  Of these, phenoxy resin and polyvinyl acetal resin are preferable as the thermoplastic resin. Accordingly, in a preferred 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% by mass to 10% by mass, more preferably 0.2% by mass to 5% by mass, and still more preferably 0.8%. 3% by mass to 1% by mass.

<(F) Curing accelerator>
In one embodiment, the resin composition of the present invention may further contain (F) a curing accelerator.

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

  Examples of phosphorus curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate. , Tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like, and triphenylphosphine and tetrabutylphosphonium decanoate are preferable.

  Examples of amine curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo. (5,4,0) -undecene and the like are mentioned, and 4-dimethylaminopyridine and 1,8-diazabicyclo (5,4,0) -undecene are preferable.

  Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 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-undecylimidazolium trimellitate, 1-cyanoethyl- 2 Phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-ethyl-4′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino- 6- [2′-Methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl- 4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl Examples include imidazole compounds such as -3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins, such as 2-ethyl-4-methylimidazole and 1-benzyl-2- Phenylimidazole is preferred.

  Commercially available products may be used as the imidazole curing accelerator, and examples thereof include “P200-H50” manufactured by Mitsubishi Chemical Corporation.

  Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) 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] Deca-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1 -Allyl biguanide, 1-phenyl biguanide, 1- ( - tolyl) biguanide, and the like, dicyandiamide, 1,5,7-triazabicyclo [4.4.0] dec-5-ene are preferred.

  As a metal type hardening accelerator, the organometallic complex or organometallic salt of metals, such as cobalt, copper, zinc, iron, nickel, manganese, tin, is mentioned, for example. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Organic zinc complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

  Although content of the hardening accelerator in a resin composition is not specifically limited, 0.01 mass%-3 mass% are preferable when the non-volatile component of an epoxy resin and a hardening | curing agent is 100 mass%.

<(G) Flame retardant>
In one embodiment, the resin composition of the present invention may contain (G) a flame retardant. Examples of the flame retardant include an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone flame retardant, and a metal hydroxide. A flame retardant may be used individually by 1 type, or may use 2 or more types together.

  Commercially available products may be used as the flame retardant, such as “HCA-HQ” manufactured by Sanko Co., Ltd., “PX-200” manufactured by Daihachi Chemical Industry Co., Ltd., and the like. As the flame retardant, those which are difficult to hydrolyze are preferable, and for example, 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide and the like are preferable.

  When the resin composition contains a flame retardant, the content of the flame retardant is not particularly limited, but is preferably 0.5% by mass to 20% by mass, more preferably 0.5% by mass to 15% by mass, and still more preferably. 0.5 mass%-10 mass% are further more preferable.

<(H) Organic filler>
In one embodiment, the resin composition of the present invention may contain (H) an organic filler. By including the component (H), the tensile fracture strength of the cured product of the resin composition layer of the resin sheet can be improved. As the organic filler, any organic filler that can be used in forming the insulating layer of the printed wiring board may be used, and examples thereof include rubber particles, polyamide fine particles, and silicone particles.

  As the rubber particles, commercially available products may be used, and examples thereof include “EXL2655” manufactured by Dow Chemical Japan, “AC3401N” and “AC3816N” manufactured by Aika Industry.

  As the rubber particles, for example, “AC3816N” and “AC3401N” manufactured by Aika Kogyo Co., Ltd. are preferable from the viewpoint that the ionicity is low and the extraction water conductivity of the cured product of the resin composition layer can be lowered.

  When the resin composition contains an organic filler, the content of the organic filler is preferably 0.1% by mass to 20% by mass, more preferably 0.2% by mass to 10% by mass, and still more preferably 0.8%. 3% by mass to 5% by mass, or 0.5% by mass to 3% by mass.

<(I) Optional additive>
In one embodiment, the resin composition of the present invention may further contain other additives as necessary. Examples of such other additives include organic copper compounds, organic zinc compounds, and organic compounds. Examples include organometallic compounds such as cobalt compounds, and resin additives such as thickeners, antifoaming agents, leveling agents, adhesion-imparting agents, and coloring agents.

<Physical properties of resin composition>
When the cured product is obtained by thermosetting the resin composition of the present invention at 100 ° C. for 30 minutes and further at 180 ° C. for 30 minutes, the contact angle of water on the surface of the cured product before roughening the surface of the cured product is determined. X (°), where Y (°) is the contact angle of the cured product surface with water after roughening the surface of the cured product, XY ≦ 0 °, preferably XY ≦ −. 3 °, more preferably XY ≦ −5 °. Although the lower limit of XY is not specifically limited, Preferably it is -50 degrees or more, More preferably, it is -40 degrees or more, More preferably, it is -30 degrees or more. By setting X−Y ≦ 0 °, the thin-film insulation is improved. XY can be measured according to the method described in <Measurement of Contact Angle> described later.

  When the cured composition is obtained by thermally curing the resin composition of the present invention at 100 ° C. for 30 minutes and further at 180 ° C. for 30 minutes, the contact angle of water on the surface of the cured product after roughening the surface of the cured product 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 further preferably 120 ° or less. By setting Y ≧ 80 °, the thin film insulation is improved. The contact angle Y can be measured according to the method described in <Measurement of Contact Angle> described later.

  When the cured composition is obtained by thermally curing the resin composition of the present invention at 100 ° C. for 30 minutes and further at 180 ° C. for 30 minutes, the contact angle of water on the surface of the cured product before roughening the surface of the cured product X is 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 further preferably 50 ° or more. By setting X <80 °, the thin-film insulation is improved. The contact angle X can be measured according to the method described in <Measurement of Contact Angle> described later.

  The roughening treatment procedure when measuring the contact angle can be performed according to the method described in <Measurement of Contact Angle> described later. In detail, it is immersed in a predetermined swelling solution at 60 ° C. for 5 minutes, then in a predetermined oxidant solution at 80 ° C. for 10 minutes, finally immersed in a neutralizing 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, and the resin composition layer is formed from the resin composition of the present invention.

  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 even more preferably 8 μm or less, from the viewpoint of reducing the thickness of the printed wiring board. Although the minimum of the thickness of a resin composition layer is not specifically limited, Usually, it may be 1 micrometer or more, 1.5 micrometers or more, 2 micrometers or more, etc.

  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 preferable.

  When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”) and polyethylene naphthalate (hereinafter abbreviated as “PEN”). .) Polyester, polycarbonate (hereinafter sometimes abbreviated as “PC”), polymethyl methacrylate (PMMA) and other acrylics, cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether Examples include ketones and polyimides. Among these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

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

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

  Moreover, as a support body, you may use the support body with a release layer which has a release layer in the surface joined to a resin composition layer. Examples of the release agent used for the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. . As the support with a release layer, a commercially available product may be used. For example, “SK-1”, “SK-1” manufactured by Lintec Corporation, which is a PET film having a release layer mainly composed of an alkyd resin release agent. “AL-5”, “AL-7”, “Lumirror T60” manufactured by Toray Industries, Inc., “Purex” manufactured by Teijin Limited, “Unipeel” manufactured by Unitika, and the like.

  Although it does not specifically limit as thickness of a support body, The range of 5 micrometers-75 micrometers is preferable, and the range of 10 micrometers-60 micrometers is more preferable. In addition, when using a support body with a release layer, it is preferable that the thickness of the whole support body with a release layer is the said range.

  The resin sheet is prepared by, for example, preparing a resin varnish in which a resin composition is dissolved in an organic solvent, applying the resin varnish on a support using a die coater or the like, and further drying to form a resin composition layer. Can be manufactured.

  Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, cellosolve and butyl carbitol, etc. Carbitols, aromatic hydrocarbons such as toluene and xylene, amide solvents such as dimethylformamide, dimethylacetamide (DMAc), and N-methylpyrrolidone. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

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

  In the resin sheet, a protective film according to the support can be further laminated on the surface of the resin composition layer that is not bonded to the support (that is, the surface opposite to the support). Although the thickness of a protective film is not specifically limited, For example, they are 1 micrometer-40 micrometers. By laminating the protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches. The resin sheet can be stored in a roll. When the resin sheet has a protective film, it can be used by peeling off the protective film.

  The resin sheet of this invention brings about the insulating layer (cured material of the resin composition layer) excellent in thin film insulation. Therefore, 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 forms an interlayer insulating layer of the printed wiring board. Therefore, it can be used more suitably as a resin sheet (resin sheet for an interlayer insulating layer of a printed wiring board). Further, for example, in a printed wiring board including a first conductor layer, a second conductor layer, and an insulating layer provided between the first conductor layer and the second conductor layer, the resin of the present invention. By forming the insulating layer with a sheet, the insulating layer between the first and second conductor layers has a thickness of 6 μm or less (preferably 5.5 μm or less, more preferably 5 μm or less), and excellent insulation performance. be able to.

  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 is provided. The plating peel strength is preferably 1.5 kgf / cm or less, more preferably 1 kgf / cm or less, and still more preferably 0.8 kgf / cm or less. The upper limit may be 0.1 kgf / cm or more. The evaluation of the plating peel strength can be measured according to the method described later (Measurement of plating adhesion (plating peel strength)).

The insulating layer formed using the resin sheet (or resin composition) of the present invention shows a good result of the insulation resistance value after elapse of 200 hours under a 130 ° C., 85 RH%, 3.3 V applied environment. That is, an insulating layer exhibiting a good insulation resistance value is provided. The upper limit of the insulation resistance value is preferably 10 ¹² Ω or less, more preferably 10 ¹¹ Ω or less, and further preferably 10 ¹⁰ Ω or less. The lower limit is not particularly limited, but is preferably 10 ⁷ Ω or more, more preferably 10 ⁸ Ω or more. The insulation resistance value can be measured according to the method described in <Evaluation of insulation reliability of insulating layer> described later.

[Printed wiring board, printed wiring board manufacturing method]
The printed wiring board of the present invention includes an insulating layer, a first conductor layer, and a second conductor layer formed of a cured product of the resin composition of the present invention. The insulating layer is provided between the first conductor layer and the second conductor layer, and insulates the first conductor layer and the second conductor layer (the conductor layer is also referred to as a wiring layer). . Since the insulating layer formed of the cured product of the resin composition of the present invention is excellent in thin film insulating properties, it is excellent in insulating properties 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, but may be 0.1 μm or more. The thickness of the insulating layer between the first and second conductor layers is the insulation between the main surface 51 of the first conductor layer 5 and the main surface 61 of the second conductor layer 6 as shown in FIG. This refers to the thickness t1 of the layer 7. 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 total thickness t2 of the 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, but may be 1 μm or more.

The printed wiring board of this invention can be manufactured by the method including the process of following (I) and (II) using the above-mentioned resin sheet.
(I) The process of laminating | stacking so that the resin composition layer of a resin sheet may join to an inner layer board | substrate on an inner layer board | substrate (II) The process of thermosetting a resin composition layer and forming an insulating layer

  The “inner layer substrate” used in step (I) is mainly a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, or one or both surfaces of the substrate. A circuit board on which a patterned conductor layer (circuit) is formed. Further, when the printed wiring board is manufactured, an inner layer circuit board of an intermediate product in which an insulating layer and / or a conductor layer is further formed is also included in the “inner layer board” in the present invention. When the printed wiring board is a circuit board with a built-in component, an inner layer board with a built-in component can be used.

  Lamination | stacking of an inner layer board | substrate and a resin sheet can be performed by heat-pressing a resin sheet to an inner layer board | substrate from the support body side, for example. Examples of the member that heat-presses the resin sheet to the inner layer substrate (hereinafter, also referred to as “heat-pressing member”) include a heated metal plate (SUS end plate) or a metal roll (SUS roll). It is preferable that the thermocompression-bonding member is not pressed directly on the resin sheet, but is pressed through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the inner layer substrate.

  Lamination of the inner layer substrate and the resin sheet may be performed by a vacuum laminating method. In the vacuum laminating method, the thermocompression bonding temperature is preferably in the range of 60 ° C to 160 ° C, more preferably 80 ° C to 140 ° C, and the thermocompression bonding pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. The thermocompression bonding time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. Lamination is preferably performed under reduced pressure conditions with a pressure of 26.7 hPa or less.

  Lamination can be performed with a commercially available vacuum laminator. Examples of the commercially available vacuum laminator include a vacuum pressure laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nikko Materials, and the like.

  After lamination, the laminated resin sheets may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression bonding member from the support side. The pressing conditions for the smoothing treatment can be the same conditions as the thermocompression bonding conditions for the laminate. The smoothing treatment can be performed with a commercially available laminator. In addition, you may perform lamination | stacking and a smoothing process continuously using said 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 cured to form an insulating layer.

  The thermosetting conditions for the resin composition layer are not particularly limited, and the conditions normally employed when forming the insulating layer of the printed wiring board may be used.

  For example, although the thermosetting conditions of the resin composition layer vary depending on the type of the resin composition, the curing temperature is in the range of 120 ° C to 240 ° C (preferably in the range of 150 ° C to 220 ° C, more preferably in the range of 170 ° C to 200 ° C.) and the curing time can be in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes 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, prior to thermosetting the resin composition layer, the resin composition layer is formed at a temperature of 50 ° C. or higher and lower than 120 ° C. (preferably 60 ° C. or higher and 110 ° C. or lower, more preferably 70 ° C. or higher and 100 ° C. or lower). Preheating may be performed for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

  When manufacturing a printed wiring board, you may further implement (III) the process of drilling in an insulating layer, (IV) the process of roughening an insulating layer, and (V) the process of forming a conductor layer. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art, which are used in the production of printed wiring boards. In addition, when removing a support body after process (II), removal of this support body is performed between process (II) and process (III), between process (III) and process (IV), or process ( It may be carried out between IV) and step (V). Moreover, if necessary, the multilayer wiring board may be formed by repeatedly forming the insulating layer and the conductor layer in the steps (II) to (V). In this case, the thickness of the insulating layer between the respective conductor layers (t1 in FIG. 1) is preferably within the above range.

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

  Step (IV) is a step of roughening the insulating layer. The procedure and conditions for the roughening treatment are not particularly limited, and known procedures and conditions that are usually used when forming an insulating layer of a printed wiring board can be employed. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order. Although it does not specifically limit as a swelling liquid, An alkaline solution, surfactant solution, etc. are mentioned, Preferably it is an alkaline solution, As this alkaline solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. Examples of commercially available swelling liquids include “Swelling Dip Securigans P” and “Swelling Dip Securigans SBU” manufactured by Atotech Japan. Although the swelling process by a swelling liquid is not specifically limited, For example, it can perform by immersing an insulating layer for 1 minute-20 minutes in 30 degreeC-90 degreeC swelling liquid. From the viewpoint of suppressing the swelling of the resin in the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40 ° C. to 80 ° C. for 5 minutes to 15 minutes. Although it does not specifically limit as an oxidizing agent, For example, the alkaline permanganate solution which melt | dissolved potassium permanganate and sodium permanganate in the aqueous solution of sodium hydroxide is mentioned. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60 to 80 ° C. for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizers include alkaline permanganate solutions such as “Concentrate Compact CP” and “Dosing Solution Securigans P” manufactured by Atotech Japan. As the neutralizing solution, an acidic aqueous solution is preferable, and as a commercially available product, for example, “Reduction Solution Securigant P” manufactured by Atotech Japan Co., Ltd. can be mentioned. The treatment with the neutralizing solution can be performed by immersing the treated surface subjected to the roughening treatment with the oxidizing agent in the neutralizing solution at 30 to 80 ° C. for 5 to 30 minutes. From the viewpoint of workability and the like, a method of immersing an object subjected to roughening treatment with an oxidizing agent in a neutralizing solution at 40 ° C. to 70 ° C. for 5 minutes to 20 minutes is preferable.

  In one embodiment, the 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 further preferably 300 nm or less. Although it does not specifically limit about a minimum, Preferably it is 0.5 nm or more, More preferably, it is 1 nm or more. The root mean square roughness Rq of the insulating layer surface after the roughening treatment is preferably 400 nm or less, more preferably 350 nm or less, and further preferably 300 nm or less. Although it does not specifically limit about a minimum, Preferably it is 0.5 nm or more, More preferably, it is 1 nm or more. The arithmetic average roughness (Ra) and root mean square roughness (Rq) of the insulating layer surface can be measured using a non-contact type surface roughness meter, and details will be described later (arithmetic average roughness (Ra)). , Measurement of root mean square roughness (Rq)).

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

  The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer is one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Contains metal. The conductor layer may be a single metal layer or an alloy layer. As the alloy layer, for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper- A layer formed from a nickel alloy and a copper / titanium alloy). Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, etc., single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel / chromium alloy, copper / An alloy layer of nickel alloy or copper / titanium alloy is preferable, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel / chromium alloy is more preferable, and a single layer of copper is preferable. A metal layer is more preferred.

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

  Although the thickness of a conductor layer is based on the design of a desired printed wiring board, generally it is 3 micrometers-35 micrometers, Preferably it is 5 micrometers-30 micrometers.

  In one embodiment, the conductor layer may be formed by plating. For example, the surface of the insulating layer can be plated by a conventionally known technique such as a semi-additive method or a full additive method to form a conductor layer having a desired wiring pattern. Hereinafter, an example in which the conductor layer is formed by a semi-additive method will be described.

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

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

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

[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 for electrical products (for example, computers, mobile phones, digital cameras, and televisions) and vehicles (for example, motorcycles, automobiles, trains, ships, and aircrafts).

  The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. The “conduction location” is a “location where an electrical signal is transmitted on a printed wiring board”, and the location may be a surface or an embedded location. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

  The semiconductor chip mounting method for manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, and no bumps. Examples include a mounting method using a build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF). Here, “a mounting method using a build-up layer without a bump (BBUL)” means “a mounting method in which a semiconductor chip is directly embedded in a recess of a printed wiring board and the semiconductor chip and wiring on the printed wiring board are connected”. It is.

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

<Measurement of average particle size of inorganic filler>
100 mg of an inorganic filler, 0.1 g of a dispersant (“SN9228” manufactured by San Nopco) and 10 g of methyl ethyl ketone were weighed in a vial and dispersed with an ultrasonic wave 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 by a batch cell method, and the average particle size by 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 fully automatic specific surface area measuring device (Macsorb HM-1210 manufactured by Mountec Co., Ltd.).

<Used inorganic filler>
Inorganic filler 1: 3,3,3-trifluoro with respect to 100 parts of spherical silica (“SPH516-05” manufactured by Nippon Steel & Sumikin Materials Co., Ltd., average particle size 0.29 μm, specific surface area 16.3 m ² / g) Surface treatment with 1 part of propyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-7103).
Inorganic filler 2: N-phenyl-3-aminopropyl with respect to 100 parts of spherical silica (“SPH516-05” manufactured by Nippon Steel & Sumikin Materials Co., Ltd., average particle size 0.29 μm, specific surface area 16.3 m ² / g) Surface treated with 1 part of trimethoxysilane (KBM573, manufactured by Shin-Etsu Chemical Co., Ltd.).
Inorganic filler 3: 3,3,3-trifluoro with respect to 100 parts of spherical silica (“UFP-30” manufactured by Denki Kagaku Kogyo Co., Ltd., average particle size 0.078 μm, specific surface area 30.7 m ² / g) Surface treated with 2 parts of propyltrimethoxysilane (KBE-7103, manufactured by Shin-Etsu Chemical Co., Ltd.).
Inorganic filler 4: N-phenyl-3-aminopropyltri to 100 parts of spherical silica (“UFP-30” manufactured by Denki Kagaku Kogyo Co., Ltd., average particle size 0.078 μm, specific surface area 30.7 m ² / g) Surface treated with 2 parts of methoxysilane (KBM573, manufactured by Shin-Etsu Chemical Co., Ltd.).
Inorganic filler 5: 100 parts of spherical silica (“SC1500SQ” (“SO-C1” surface-treated with hexamethyldisilazane) manufactured by Admatechs Co., Ltd.), average particle size 0.63 μm, specific surface area 11.2 m ² / g) In contrast, N-phenyl-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM573) was surface treated with 1 part.

[Preparation of resin composition]
<Preparation of Resin Composition 1>
6 parts of bixylenol type epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185), 10 parts of naphthalene type epoxy resin (“ESN475V” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., about 332), bisphenol AF type epoxy resin ( Mitsubishi Chemical Corporation "YL7760", epoxy equivalent of about 238) 10 parts, bisphenol type epoxy resin (Nippon Steel & Sumikin Chemical Co., Ltd. "ZX1059", epoxy equivalent of about 169, bisphenol A type and bisphenol F type 1: 1 mixture) 4 2 parts of phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Corporation, 1: 1 solution of cyclohexanone: methyl ethyl ketone (MEK) having a solid content of 30% by mass) is stirred in a mixed solvent of 20 parts of solvent naphtha and 10 parts of cyclohexanone. It was dissolved by heating. After cooling to room temperature, there were 3 parts of a triazine skeleton-containing novolak curing agent (“LA7054” manufactured by DIC, MEK solution having a hydroxyl equivalent weight of about 125 and a solid content of 60%), and a naphthol curing agent (manufactured by DIC “ SN-495V ”, hydroxyl equivalent of about 231) 6 parts, inorganic filler 1 90 parts, amine curing accelerator (4-dimethylaminopyridine (DMAP)) 0.05 part, and uniformly mixed with a high-speed rotary mixer After the dispersion, the resin composition 1 was prepared by filtering with a cartridge filter (“SHP020” manufactured by ROKITETECHNO).

<Preparation of resin composition 2>
6 parts of bixylenol type epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185), 10 parts of naphthalene type epoxy resin (“ESN475V” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., about 332), bisphenol AF type epoxy resin ( Mitsubishi Chemical Corporation "YL7760", epoxy equivalent of about 238) 10 parts, bisphenol type epoxy resin (Nippon Steel & Sumikin Chemical Co., Ltd. "ZX1059", epoxy equivalent of about 169, bisphenol A type and bisphenol F type 1: 1 mixture) 4 2 parts of phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Corporation, 1: 1 solution of cyclohexanone: methyl ethyl ketone (MEK) having a solid content of 30% by mass) is stirred in a mixed solvent of 20 parts of solvent naphtha and 10 parts of cyclohexanone. It was dissolved by heating. After cooling to room temperature, there are 4 parts of a triazine skeleton-containing cresol novolac-based curing agent (“LA3018-50P” manufactured by DIC, hydroxyl group equivalent of about 151, 2-methoxypropanol solution with a solid content of 50%), active ester system 7 parts of curing agent (“EXB-8000L-65M” manufactured by DIC, MEK solution having an active group equivalent of about 220 and 65% by mass of non-volatile components), 90 parts of inorganic filler 2, amine-based curing accelerator (4-dimethylamino) 0.05 part of pyridine (DMAP) was mixed and dispersed uniformly with a high-speed rotary mixer, and then filtered through a cartridge filter (“SHP020” manufactured by ROKITECHNO) to prepare Resin Composition 2.

<Preparation of resin composition 3>
6 parts of bixylenol type epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185), 20 parts of naphthalene type epoxy resin (“ESN475V” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., about 332), naphthylene ether type epoxy resin 2 parts (“EXA-731-G4” manufactured by DIC, epoxy equivalent of about 213) were dissolved by heating in a mixed solvent of 20 parts of solvent naphtha and 10 parts of cyclohexanone with stirring. After cooling to room temperature, there are 4 parts of a triazine skeleton-containing cresol novolac-based curing agent (“LA3018-50P” manufactured by DIC, hydroxyl group equivalent of about 151, 2-methoxypropanol solution with a solid content of 50%), active ester system 7 parts of curing agent ("EXB-8000L-65M" manufactured by DIC, MEK solution having an active group equivalent of about 220 and 65% by mass of non-volatile components), 50 parts of inorganic filler 3, imidazole-based curing accelerator (1B2PZ, 1- 0.05 part of (benzyl-2-phenylimidazole) was mixed and dispersed uniformly with a high-speed rotary mixer, and then filtered through a cartridge filter (“SHP020” manufactured by ROKITECHNO) to prepare Resin Composition 3.

<Preparation of resin composition 4>
6 parts of bixylenol type epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185), 10 parts of naphthalene type epoxy resin (“ESN475V” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., about 332), bisphenol AF type epoxy resin ( 10 parts “YL7760” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 238), 2 parts of naphthylene ether type epoxy resin (“EXA-7311-G4” manufactured by DIC, epoxy equivalent of about 213), 20 parts of solvent naphtha and 10 of cyclohexanone The mixture was heated and dissolved in a part of the mixed solvent with stirring. After cooling to room temperature, there are 4 parts of a triazine skeleton-containing cresol novolac-based curing agent (“LA3018-50P” manufactured by DIC, hydroxyl group equivalent of about 151, 2-methoxypropanol solution with a solid content of 50%), active ester system 7 parts of curing agent (“EXB-8000L-65M” manufactured by DIC, MEK solution with active group equivalent of about 220, 65% by mass of non-volatile component), 50 parts of inorganic filler 4 and amine-based curing accelerator (4-dimethylamino) 0.05 parts of pyridine (DMAP) was mixed and dispersed uniformly with a high-speed rotary mixer, and then filtered through a cartridge filter (“SHP020” manufactured by ROKITECHNO) to prepare Resin Composition 4.

<Preparation of resin composition 5>
6 parts of bixylenol type epoxy resin (Mitsubishi Chemical “YX4000HK”, epoxy equivalent of about 185), 20 parts of naphthalene type epoxy resin (“NSN475V” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., about 332), cyclohexane type epoxy resin (Mitsubishi) 4 parts of “ZX1658GS” manufactured by Kagaku Co., Ltd., having an epoxy equivalent of about 135) was dissolved by heating in a mixed solvent of 20 parts of solvent naphtha and 10 parts of cyclohexanone with stirring. After cooling to room temperature, there were 3 parts of a triazine skeleton-containing novolak curing agent (“LA7054” manufactured by DIC, MEK solution having a hydroxyl equivalent weight of about 125 and a solid content of 60%), and a naphthol curing agent (manufactured by DIC “ SN-495V ", hydroxyl equivalent of about 231) 6 parts, inorganic filler 5 80 parts, amine curing accelerator (4-dimethylaminopyridine (DMAP)) 0.05 part, and uniformly mixed with a high-speed rotary mixer After the dispersion, the resin composition 5 was prepared by filtering with a cartridge filter (“SHP020” manufactured by ROKITECHNO).

<Preparation of resin composition 6>
6 parts of bixylenol type epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185), 20 parts of naphthalene type epoxy resin (“ESN475V” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., about 332), naphthylene ether type epoxy resin ("EXA-7311-G4" manufactured by DIC, epoxy equivalent of about 213), 2 parts, phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, 1: 1 solution of cyclohexanone: methyl ethyl ketone (MEK) having a solid content of 30% by mass) The part was dissolved by heating in a mixed solvent of 20 parts of solvent naphtha and 10 parts of cyclohexanone while stirring. After cooling to room temperature, there are 4 parts of a triazine skeleton-containing cresol novolac-based curing agent (“LA3018-50P” manufactured by DIC, hydroxyl group equivalent of about 151, 2-methoxypropanol solution with a solid content of 50%), active ester system 7 parts of curing agent ("EXB-8000L-65M" manufactured by DIC, MEK solution having an active group equivalent of about 220 and 65% by mass of non-volatile components), 80 parts of inorganic filler 5, imidazole-based curing accelerator (1B2PZ, 1- 0.05 part of (benzyl-2-phenylimidazole) was mixed and dispersed uniformly with a high-speed rotary mixer, and then filtered through a cartridge filter (“SHP020” manufactured by ROKITECHNO) to prepare Resin Composition 6.

The components used for the preparation of the resin compositions 1 to 6 and their blending amounts (parts by weight of nonvolatile content) are shown in the following table. The abbreviations in the table below are as follows.
YX4000HK: Boxylenol type epoxy resin, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185
ESN475V: Naphthalene type epoxy resin, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 332
YL7760: Bisphenol AF type epoxy resin, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 238
EXA-7311-64: naphthylene ether type epoxy resin, manufactured by DIC, epoxy equivalent of about 213
ZX1059: bisphenol type epoxy resin, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 169, 1: 1 mixture of bisphenol A type and bisphenol F type ZX1658GS: cyclohexane type epoxy resin, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 135
LA3018-50P: Triazine skeleton-containing cresol novolak-based curing agent, manufactured by DIC, hydroxyl equivalent of about 151, 2-methoxypropanol solution having a solid content of 50% LA7054: Triazine skeleton-containing novolak-based curing agent, manufactured by DIC, hydroxyl equivalent of about 125 , 60% solid MEK solution SN-495V: naphthol-based curing agent, manufactured by DIC, hydroxyl equivalent of about 231
EXB-8000L-65M: Active ester type curing agent, manufactured by DIC, active group equivalent of about 220, MEK solution YX7553BH30 with 65% by mass of non-volatile components: Phenoxy resin, manufactured by Mitsubishi Chemical Co., Ltd., cyclohexanone with a solid content of 30% by mass: methyl ethyl ketone ( MEK) 1: 1 solution DMAP: amine-based curing accelerator, 4-dimethylaminopyridine 1B2PZ: imidazole-based curing accelerator, 1-benzyl-2-phenylimidazole

[Production of resin sheet]
As a support, a PET film (“Lumirror R80” manufactured by Toray Industries, Inc., thickness 38 μm, softening point 130 ° C., “release PET”) subjected to release treatment with an alkyd resin release agent (“AL-5” manufactured by Lintec) Prepared.

  Each resin composition was uniformly applied with a die coater so that the thickness of the resin composition layer after drying was 13 μm on the release PET, and dried at 70 ° C. to 95 ° C. for 2 minutes, thereby releasing the release PET. A resin composition layer was obtained on top. Next, a rough surface of a polypropylene film (“Alphan MA-411” manufactured by Oji F-Tex Co., Ltd., thickness 15 μm) as a protective film is bonded to the resin composition layer on the surface not bonded to the support of the resin sheet. Laminated. This obtained the resin sheet which consists of order of mold release PET (support body), a resin composition layer, and a protective film.

[Evaluation test]
<Measurement of roughness and plating peel strength>
(Preparation of evaluation substrate)
(1) Ground treatment of inner layer circuit board As an inner layer circuit board, a glass cloth base epoxy resin double-sided copper-clad laminate having circuit conductors (copper) formed on both sides with a wiring pattern of L / S = 2 μm / 2 μm ( A copper foil thickness of 3 μm, a substrate thickness of 0.15 mm, and “HL832NSF LCA” (255 × 340 mm size) manufactured by Mitsubishi Gas Chemical Company, Inc. were prepared. Both surfaces of the inner layer circuit board were subjected to organic coating treatment on the copper surface with “FlatBOND-FT” manufactured by MEC.

(2) Lamination of resin sheet The protective film is peeled off from each resin sheet produced in the examples and comparative examples, and a batch type vacuum pressure laminator (manufactured by Nikko Materials, 2-stage buildup laminator, CVP700) is used. Lamination was performed on both surfaces of the inner layer circuit board so that the resin composition layer was in contact with the inner layer circuit board. Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and pressing for 45 seconds at 130 ° C. and a pressure of 0.74 MPa. Next, hot pressing was performed at 120 ° C. and a pressure of 0.5 MPa for 75 seconds.

(3) Thermosetting of resin composition layer The inner layer circuit board on which the resin sheet is laminated is placed in an oven at 100 ° C. for 30 minutes, then transferred to an oven at 180 ° C. and then thermoset for 30 minutes to obtain a thickness. A 5 μm insulating layer was formed, and the release PET was peeled off. This is referred to as “evaluation substrate A”.

(4) Step of performing roughening treatment A desmear treatment as a roughening treatment was performed on the evaluation substrate A on which the insulating layer was formed. In addition, as a desmear process, the following wet desmear process was implemented.

Wet desmear treatment:
Swelling solution (“Swelling Dip Securigant P” manufactured by Atotech Japan Co., Ltd., aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60 ° C. for 5 minutes, then oxidant solution (“Concentrate Compact CP” manufactured by Atotech Japan Co., Ltd.) , Aqueous solution with potassium permanganate concentration of about 6% and sodium hydroxide concentration of about 4%) at 80 ° C. for 10 minutes, and finally into neutralization solution (“Reduction Solution Securigant P”, sulfuric acid aqueous solution manufactured by Atotech Japan) After dipping at 40 ° C. for 5 minutes, it was dried at 80 ° C. for 15 minutes.

(5) Step of forming a conductor layer (5-1) Electroless plating step In order to form a conductor layer on the surface of the circuit board, a plating step including the following steps 1 to 6 (using chemicals manufactured by Atotech Japan) The copper plating step) was performed to form a conductor layer.

1. Alkali cleaning (cleaning and charge adjustment of the surface of the insulating layer with via holes)
Product name: Cleaned at 60 ° C. for 5 minutes using Cleaning Cleaner Security 902 (trade name).
2. Soft etching (cleaning inside via holes)
The mixture was treated with an aqueous sodium peroxodisulfate solution at 30 ° C. for 1 minute.
3. Pre-dip (adjustment of surface charge of insulating layer for Pd application)
Pre. Using Dip Neoganth B (trade name), it was treated at room temperature for 1 minute.
4). Activator application (Pd application 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 applied to the insulating layer)
Reducer Neoganth WA (trade name) and Reducer Accelerator 810 mod. Using a mixed solution with (trade name), it was treated at 30 ° C. for 5 minutes.
6). Electroless copper plating process (Cu is deposited on the surface of the insulating layer (Pd surface))
Using a mixture of Basic Solution Print MSK-DK (trade name), Copper solution Print MS MS (trade name), Stabilizer Printganth MSK-DK (trade name), and Reducer Cu (trade name) at 35 ° C. Treated for 20 minutes. The thickness of the formed electroless copper plating layer was 0.8 μm.

(5-2) Electrolytic plating process Subsequently, the electrolytic copper plating process was performed on the conditions with which a via hole is filled with copper using the chemical solution made from Atotech Japan. Thereafter, as a resist pattern for patterning by etching, a land pattern having a diameter of 1 mm conducted to the via hole and a circular conductor pattern having a diameter of 10 mm not connected to the lower layer conductor are used to form a thickness of 10 μm on the surface of the insulating layer. A conductor layer having lands and conductor patterns was formed. Next, annealing was performed at 200 ° C. for 90 minutes. This substrate was designated as “evaluation substrate B”.

(Measurement of arithmetic average roughness (Ra), root mean square roughness (Rq))
The surface of the insulating layer outside the circular conductor pattern of the evaluation substrate B is obtained by using a non-contact type surface roughness meter (WYKO NT3300, manufactured by Becoins Instruments Co., Ltd.) with a VSI contact mode and a 50 × lens as a measurement range of 121 μm × 92 μm. Ra values and Rq values were obtained from the obtained numerical values. The average value of 6 points was calculated for each, and the result of rounding off the last digit was shown in the table below.

(Measurement of plating adhesion (plating peel strength))
Cut the 10mm width and 100mm length into the conductor layer of the evaluation board B, peel off one end of the conductor layer, and use a gripping tool (manufactured by TS E Co., Ltd., Autocom type testing machine AC-50C-SL). Using a Instron universal testing machine, the load (kgf / cm) when 35 mm was peeled in the vertical direction at a speed of 50 mm / min at room temperature was measured, and the peel strength was obtained.

<Measurement of insulation layer thickness between conductor layers>
The evaluation substrate B was subjected to cross-sectional observation using an FIB-SEM composite device (“SMI3050SE” manufactured by SII Nanotechnology). Specifically, the cross section in the direction perpendicular to the surface of the conductor layer was cut out by FIB (focused ion beam), and the insulating layer thickness between the conductor layers was measured from the cross section SEM image. For each sample, five cross-sectional SEM images selected at random were observed, and the average value was defined as the thickness (μm) of the insulating layer between the conductor layers, and is shown in the following table.

<Evaluation of insulation reliability of insulating layer>
The highly accelerated life test apparatus (with the 10 mm diameter circular conductor side of the evaluation substrate B obtained above as the + electrode and the grid conductor (copper) side of the inner layer circuit board connected to the 1 mm diameter land as the − electrode) Using an ETAC "PM422"), the insulation resistance value after passing 200 hours under conditions of 130 ° C, 85% relative humidity, and 3.3V DC voltage was applied to an electrochemical migration tester (manufactured by J-RAS). “ECM-100”). This measurement is performed 6 times. In all six test pieces, when the resistance value is 10 ⁷ Ω or more, “◯” is indicated, and when any one is less than 10 ⁷ Ω, “X” is indicated, and the evaluation result and the insulation resistance value are obtained. Are shown in the table below. The insulation resistance values listed in the table below are the minimum insulation resistance values of the six test pieces.

<Measurement of contact angle>
The contact angle of the water droplet on the cured product surface by the droplet method was measured using an automatic contact angle meter (DropMaster DMs-401 manufactured by Kyowa Interface Science Co., Ltd.). Specifically, pure water was filled in a syringe to produce 1.0 μL of water droplets, which were attached to the insulating layer surface of the evaluation substrate A. The contact angle after 2000 ms after adhering a water droplet was measured with the above-mentioned automatic contact angle meter, and was taken as X (°).

  Subsequently, the roughening process of the insulating layer in the evaluation substrate A was performed in the same manner as in the step (4) of performing the roughening process. Thereafter, pure water was filled in a syringe to produce 1.0 μL of water droplets, which were attached to the surface of the insulating layer subjected to the roughening treatment of the evaluation substrate A. The contact angle after 2000 ms after adhering a water droplet was measured with the above-mentioned automatic contact angle meter, and was defined as Y (°). The case where XY was 0 or less was “◯”, and the case where XY exceeded 0 was “x”. Moreover, the case where Y is 80 ° or more is “◯”, and the case where Y is less than 80 ° is “×”.

5 1st conductor layer 51 principal surface 6 of 1st conductor layer 2nd conductor layer 61 principal surface 7 of 2nd conductor layer 7 insulating layer

Claims (14)

(A) an epoxy resin, and (B) a resin composition containing a curing agent,
When a cured product was obtained by thermosetting the resin composition at 100 ° C. for 30 minutes and further at 180 ° C. for 30 minutes, the contact angle of the cured product surface with water before roughening the surface of the cured product was X (° ), And when the contact angle of water on the surface of the cured product after roughening the surface of the cured product is Y (°),
A resin composition satisfying the relationship of XY ≦ 0 ° and Y ≧ 80 °.   The resin composition according to claim 1, further comprising (C) an inorganic filler.   The resin composition according to claim 2, wherein the content of the component (C) is 50% by mass or more when the nonvolatile component in the resin composition is 100% by mass.   (C) The resin composition of Claim 2 or 3 whose average particle diameter of a component is 0.05 micrometer-0.35 micrometer.   The resin composition of any one of Claims 1-4 containing a fluorine compound.   The resin composition according to claim 5, wherein the fluorine compound is a fluorine-containing epoxy resin.   The resin composition according to claim 5 or 6, wherein the fluorine compound is (D) a fluorine-containing silane coupling agent.   The resin composition according to claim 7, wherein the component (C) is surface-treated with the component (D).   The resin composition according to any one of claims 1 to 8, which is used for forming an insulating layer of a printed wiring board.   The resin sheet containing the resin composition layer formed with the support body and the resin composition of any one of Claims 1-9 provided on this support body.   The resin sheet according to claim 10, wherein the resin composition layer has a thickness of 15 μm or less.   The insulation of a printed wiring board comprising: a first conductor layer; a second conductor layer; and an insulating layer formed between the first conductor layer and the second conductor layer and having a thickness of 6 μm or less. The resin sheet according to claim 11, which is for layer formation. 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 printed wiring board, wherein the insulating layer is a cured product of the resin composition according to any one of claims 1 to 9.   A semiconductor device comprising the printed wiring board according to claim 13.

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