JP6766507B2 - Resin composition - Google Patents

Description

The present invention relates to resin compositions. 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 the inner layer substrate and the insulating layer, for example, the resin composition for a thin film described in Patent Document 1 is known.

Japanese Unexamined Patent Publication No. 2014-152309

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 is proposed that the blending amount of the thermoplastic resin be a predetermined amount. However, in this document, the insulation performance (hereinafter, also referred to as "thin film insulating property") when the thickness of the insulating layer is reduced has not been studied at all.

When the insulating layer is a thin film, the inorganic filler particles come into contact with each other and a current easily flows through the interface, or the thin insulating layer increases the capacitance and makes it easy to short-circuit. For example, it becomes more difficult to maintain the insulation performance than the conventional one.

An object of the present invention is a resin composition capable of imparting a thin insulating layer having excellent insulating performance; a resin sheet containing the resin composition; a printed wiring board provided with a thin insulating layer having excellent insulating performance, and a semiconductor device. To provide.

As a result of diligent studies to solve the above problems, the present inventors have determined the contact angle of the surface of the cured product of the resin composition with water before the roughening treatment of the cured product and after the roughening treatment of the cured product of the resin composition. We have found that the thin film insulation property is improved by setting the contact angle of the cured product surface with water within a specific range, and have completed the present invention.

That is, the present invention includes the following contents.
[1] A resin composition containing (A) an epoxy resin and (B) a curing agent.
When the resin composition was heat-cured at 100 ° C. for 30 minutes and further at 180 ° C. for 30 minutes to obtain a cured product, the contact angle of the cured product surface with water before roughening the surface of the cured product was set to X (°). ), And when the contact angle of the cured product surface with water after roughening the cured product surface is Y (°),
A resin composition satisfying the relationship of XY ≦ 0 ° and Y ≧ 80 °.
[2] The resin composition according to [1], which further contains (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 non-volatile component in the resin composition is 100% by mass.
[4] The resin composition according to [2] or [3], wherein the average particle size 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 used for forming an insulating layer of a printed wiring board.
[10] A resin sheet comprising a support and a resin composition layer provided on the support and formed of the resin composition according to any one of [1] to [9].
[11] The resin sheet according to [10], wherein the thickness of the resin composition layer is 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. hand,
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 imparting a thin insulating layer having excellent insulating performance; a resin sheet containing the resin composition; a printed wiring board provided with a thin insulating layer having excellent 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, the resin sheet, the printed wiring board, and the semiconductor device of the present invention will be described in detail.

[Resin composition]
The resin composition of the present invention is a resin composition containing (A) an epoxy resin and (B) a curing agent, and the resin composition is thermoset 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 the cured product surface is roughened is set to X (°), and the contact angle of the cured product surface with water after the cured product surface is roughened is set to X (°). 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 as to satisfy the relationship of XY ≦ 0 ° and Y ≧ 80 °, the surface of the insulating layer is made hydrophobic, so that moisture or the like permeates into the insulating layer. It becomes possible to provide a thin insulating layer having excellent insulating performance by making it difficult to perform. 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 of the surface of the cured product before roughening treatment with water is referred to as “contact angle X”. Therefore, 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 of the surface of the cured product after the roughening treatment with water is "contact". Sometimes called "Kaku Y".
Here, the contact angle means the angle formed by the liquid surface and the solid surface (taking the angle inside the liquid) at the place where the free surface of the stationary liquid comes into contact with the solid wall.

The resin composition further contains (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), if necessary. ) It may contain an additive such as an organic filler. Further, the resin composition of the present invention preferably contains a fluorine compound from the viewpoint of adjusting the contact angle X and the contact angle Y within desired ranges. The fluorine compound is a compound containing one or more fluorine atoms per molecule, and is a concept including an organic compound and an inorganic compound. The weight average molecular weight of the fluorine compound is usually 100 to 5000. The fluorine compound is preferably contained as any of the components (A) to (H), and the fluorine compound is preferably contained as the component (A) and / or as the component (D). The fluorine compound may be used alone or in combination of two or more. When the fluorine compound is contained as the component (A), the component (A) may be used in combination with the fluorine compound and the component (A) which is not a fluorine compound. Hereinafter, each component contained in the resin composition of the present invention will be described in detail.

<(A) Epoxy resin>
Examples of the (A) epoxy resin include fluorine-containing epoxy resins such as bisphenol AF type epoxy resin and perfluoroalkyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and dicyclo. Pentaziene type epoxy resin, trisphenol type epoxy resin, naphthol novolac type epoxy resin, phenol novolac 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, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy Examples thereof include resins, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resins, trimethylol type epoxy resins, and tetraphenylethane type epoxy resins. One type of epoxy resin may be used alone, or two or more types may be used in combination.

The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. When the non-volatile 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, an epoxy resin having two or more epoxy groups in one molecule and liquid at a temperature of 20 ° C. (hereinafter referred to as "liquid epoxy resin") 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, it has excellent flexibility and the breaking strength of the cured product is also improved.

Examples of the liquid epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolac type epoxy resin, and ester skeleton. The alicyclic epoxy resin, cyclohexanedimethanol type epoxy resin, glycidylamine type epoxy resin, and epoxy resin having a butadiene structure are preferable, and glycidylamine type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, and 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, and "828US" and "jER828EL" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation. , "JER807" (bisphenol F type epoxy resin), "jER152" (phenol novolac type epoxy resin), "YL7760" (bisphenol AF type epoxy resin), "630", "630LSD" (glycidylamine type epoxy resin), Nippon Steel "ZX1059" manufactured by Sumikin Chemical Co., Ltd. (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin), "YD-8125G" manufactured by Nippon Steel Sumikin Chemical Co., Ltd. (bisphenol A type epoxy resin), "Nagase Chemtex" EX-721 "(glycidyl ester type epoxy resin), Daicel's" celloxide 2021P "(alicyclic epoxy resin having an ester skeleton)," PB-3600 "(epoxy resin having a butadiene structure), Nippon Steel Chemical Co., Ltd. "ZX1658", "ZX1658GS" (liquid 1,4-glycidylcyclohexane) manufactured by Mitsubishi Chemical Co., Ltd. "630LSD" (glycidylamine type epoxy resin) manufactured by Daikin Industries, Ltd. "E-7432", "E-" 7632 ”(perfluoroalkyl type epoxy resin) and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the solid epoxy resin 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, and 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), and "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 Kayakusha ( Trisphenol type epoxy resin), "NC7000L" (naphthol novolac type epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin), "ESN475V" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. Naphthalene type epoxy resin), "ESN485" (naphthol novolac type epoxy resin), Mitsubishi Chemical Co., Ltd. "YX4000H", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bixilenol type epoxy resin), "YX8800" (Anthracen type epoxy resin), Osaka Gas Chemical Co., Ltd. "PG-100", "CG-500", Mitsubishi Chemical Co., Ltd. "YL7800" (fluorene type epoxy resin), Mitsubishi Chemical Co., Ltd. "jER1010", ( Solid bisphenol A type epoxy resin), "jER1031S" (tetraphenylethane type epoxy resin) and the like can be mentioned.

The liquid epoxy resin has two or more epoxy groups in one molecule, and an aromatic epoxy resin that is liquid at a temperature of 20 ° C. is preferable, and the solid epoxy resin has three or more epoxy groups in one molecule. A solid aromatic epoxy resin having a temperature of 20 ° C. is preferable. The aromatic epoxy resin in the present invention means an epoxy resin having an aromatic ring structure in its molecule.

The component (A) is preferably a fluorine-containing epoxy resin, which is a fluorine compound, from the viewpoint of adjusting the contact angle X and the contact angle Y within desired ranges.

When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, their quantity ratio (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.1 to 1:15 in terms of mass ratio. preferable. By setting the amount ratio of the liquid epoxy resin to the solid epoxy resin within such a range, i) when used in the form of a resin sheet, appropriate adhesiveness is provided, and ii) when used in the form of a resin sheet. Sufficient flexibility can be obtained, handleability is improved, and iii) a cured product of the resin composition layer having sufficient breaking strength can be obtained. From the viewpoint of the effects of i) to iii) above, the amount ratio of the liquid epoxy resin to the 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, still more preferably 13% by mass, from the viewpoint of obtaining an insulating layer exhibiting good tensile strength and insulation reliability. % Or more. The upper limit of the content of the epoxy resin is not particularly limited as long as the effect of the present invention is exhibited, but is preferably 50% by mass or less, more preferably 40% by mass or less.

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

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 It is preferably 1 to 5, more preferably 1 to 5, and even more preferably 1 to 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. Within this range, the crosslink density of the cured product of the resin composition layer becomes 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 the resin containing 1 equivalent of the epoxy group.

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

<(B) Hardener>
The curing agent is not particularly limited as long as it has a function of curing the epoxy resin. For example, a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, a benzoxazine-based curing agent, and a cyanate ester-based curing agent. Examples thereof include a curing agent and a carbodiimide-based curing agent. The curing agent may be used alone or in combination of two or more.

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. Further, from the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent is more preferable. Of 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-7851" manufactured by Meiwa Kasei Co., Ltd., and "NHN" manufactured by Nippon Kayaku Co., Ltd. "CBN", "GPH", "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V", "SN375", "SN395" manufactured by Nippon Steel & Sumitomo Metal Corporation , DIC Corporation "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500" and the like.

The active ester-based curing agent is not particularly limited, but generally contains one molecule of an ester group having high reactive activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. A compound having two or more of them is preferably used. The active ester-based 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-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester-based 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, pyromellitic acid and the like. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenol phthaline, 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, fluoroglusin, Examples thereof include benzenetriol, dicyclopentadiene-type diphenol compounds, and phenol novolac. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two phenol molecules with one dicyclopentadiene molecule.

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 phenol novolac, and an active ester compound containing a benzoylated product of phenol novolac are preferable. Of these, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene-type diphenol structure are more preferable. The "dicyclopentadiene-type diphenol structure" represents a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

Commercially available products of active ester-based curing agents include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", and "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" (manufactured by DIC) as an active ester compound containing an acetylated product of phenol novolac. Mitsubishi Chemical Co., Ltd.), "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester compound containing a benzoylated product of phenol novolac, "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester-based curing agent which is an acetylated product of phenol novolac. Examples of the active ester-based curing agent which is a benzoylated product of phenol novolac include "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), and "YLH1048" (manufactured by Mitsubishi Chemical Corporation).

Specific examples of the benzoxazine-based curing agent include "HFB2006M" manufactured by Showa High Polymer Co., Ltd., "Pd" and "FA" manufactured by Shikoku Chemicals Corporation.

Examples of the cyanate ester-based curing agent include bisphenol A disicianate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis (2,6-dimethylphenylcyanate), and 4,4. '-Etilidene diphenyl disianate, hexafluorobisphenol A disyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanate phenylmethane), 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 Examples thereof include polyfunctional cyanate resins derived from novolak and cresol novolak, and prepolymers in which these cyanate resins are partially triazined. Specific examples of the cyanate ester-based curing agent include "PT30" and "PT60" (phenol novolac type polyfunctional cyanate ester resin), "ULL-950S" (polyfunctional cyanate ester resin), and "BA230" manufactured by Ronza Japan. , "BA230S75" (a prepolymer in which part or all of bisphenol A disyanate is triazined to form a trimer) and the like.

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

The amount ratio of the epoxy resin to the curing agent is a ratio of [total number of epoxy groups in the epoxy resin]: [total number of reactive groups in the curing agent], preferably in the range of 1: 0.01 to 1: 2. 1: 0.015 to 1: 1.5 is more preferable, and 1: 0.02 to 1: 1 is even more preferable. Here, the reactive group of the curing agent is an active hydroxyl group, an active ester group, or the like, and differs depending on the type of the curing agent. The total number of epoxy groups in the epoxy resin is the total number of all epoxy resins obtained by dividing the solid content mass of each epoxy resin by the epoxy equivalent, and the total number of reactive groups in the curing agent is The value obtained by dividing the solid content mass of each curing agent by the reaction group equivalent is the total value for all the curing agents. By setting the amount ratio of the epoxy resin and the curing agent within such a range, the heat resistance of the cured product of the resin composition layer is further improved.

In one embodiment, the resin composition comprises the epoxy resin and curing agent described above. The resin composition is (A) a mixture of a liquid epoxy resin and a solid epoxy resin as the epoxy resin (the mass ratio of the liquid epoxy resin: the solid epoxy resin is preferably 1: 0.1 to 1:15, more preferably. 1: 0.3 to 1:12, more preferably 1: 0.6 to 1:10) as (B) a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, and a cyanate ester-based curing agent. It is preferable to contain one or more selected from the group consisting of curing agents (preferably one or more selected from the group consisting of active ester-based curing agents and cyanate ester-based curing agents).

The content of the curing agent in the resin composition is not particularly limited, but is preferably 30% by mass or less, more preferably 25% by mass or less, and further preferably 20% by 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, but 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 , Zirconate oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconate titanate, zirconate titnate phosphate and the like. Of these, silica is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica and the like. Further, as silica, spherical silica is preferable. The inorganic filler may be used alone or in combination of two or more.

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. The lower limit of the average particle size is preferably 0.05 μm or more, more preferably 0.06 μm or more, still more preferably 0.07 μm or more, from the viewpoint of improving the dispersibility in the resin composition layer. Examples of commercially available inorganic fillers having such an average particle size include "UFP-30" manufactured by Denki Kagaku Kogyo Co., Ltd. and "SPH516-05" manufactured by Nippon Steel & Sumikin Materials Co., Ltd. By adjusting the average particle size of the inorganic filler within the above range, the insulating property can be improved.

The average particle size of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, it can be measured by creating a particle size distribution of the inorganic filler on a volume basis with a laser diffraction / scattering type particle size distribution measuring device and using the median diameter as the average particle size. As the measurement sample, an inorganic filler dispersed in methyl ethyl ketone by ultrasonic waves can be preferably used. As the laser diffraction / scattering type particle size distribution measuring device, "LA-500" manufactured by HORIBA, Ltd., "SALD-2200" manufactured by Shimadzu Corporation, or the like 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, may be referred to as “another surface treatment agent”). The component (C) may be surface-treated with the component (D) or may be surface-treated with another surface treatment agent, and the component (C) may be surface-treated from the viewpoint of adjusting the contact angle X and the contact angle Y. Is preferably surface-treated with the component (D). One type of surface treatment agent may be used alone, or two or more types may be used in combination.

As the other surface treatment agent, at least one surface treatment agent such as 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-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, silane-based coupling agents, organosilazane compounds, titanate-based 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., and Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical 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.

From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment with the surface treatment agent is such that the surface treatment is performed with 0.2 parts by mass to 2 parts by mass of the surface treatment agent with respect to 100 parts by mass of the component (C). It is preferable that the surface is treated with 0.2 parts by mass to 1 part by mass, and the surface is preferably treated with 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, from the viewpoint of suppressing an increase in the melt viscosity of the resin varnish and the melt viscosity in the sheet form, 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 further preferable. 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 a surface treatment agent, and ultrasonic cleaning is performed at 25 ° C. for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon 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. or the like can be used.

The content (filling amount) of the inorganic filler in the resin composition is preferably 50% by mass when the non-volatile component in the resin composition is 100% by mass from the viewpoint of improving the thickness stability of the resin composition layer. % Or more, more preferably 55% by mass or more, 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 improving the thin film insulating property and the tensile breaking 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. By containing a fluorine-containing silane coupling agent, the contact angle X and the contact angle Y can be adjusted.

Specific examples of the component (D) include "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. The component (D) may be used alone or in combination of two or more.

The mode of the component (D) contained in the resin composition of the present invention is not particularly limited, but it is preferably contained in the resin composition in the following modes (i) to (iii), and is preferably (i) or (ii). It is more preferable to contain it in the resin composition in the aspect of (i), and it is further preferable to contain it in the resin composition in the aspect of (i). That is, the component (D) is preferably contained in the resin composition as a surface treatment agent for the component (C).
(I) The component (D) is contained as a surface treatment agent for the component (C).
(Ii) (D) component alone is contained 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.
"The component (D) is contained as a surface treatment agent for the component (C)" means that the component (C) is surface-treated with the component (D). In this case, component (D) is usually on the surface of component (C). Further, "containing the component (D) alone in the resin composition" means that the component (D) is not contained as a surface treatment agent for the component (C). When the component (D) is not contained as a surface treatment agent for the component (C), the component (C) is liberated 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. The upper limit is not particularly limited, but is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less.

When the component (D) is contained as a surface treatment agent for the component (C), the degree of surface treatment with the surface treatment agent is based on 100 parts by mass of the component (C) from the viewpoint of improving the dispersibility of the inorganic filler. The surface treatment is preferably performed with 0.2 parts by mass to 2 parts by mass, preferably 0.2 parts by mass to 1 part by mass, and 0.3 parts by mass to 0. It is preferable that the surface is treated with 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 thereof include ether ketone resin and polyester resin, and phenoxy resin is preferable. The thermoplastic resin may be used alone or in combination of two or more.

The polystyrene-equivalent weight average molecular weight of the thermoplastic resin is preferably in the range of 8,000 to 70,000, more preferably in the range of 10,000 to 60,000, and even more preferably in the range of 20,000 to 60,000. The polystyrene-equivalent weight average molecular weight of the thermoplastic resin is measured by gel permeation chromatography (GPC). Specifically, the polystyrene-equivalent weight average molecular weight of the thermoplastic resin is determined by using LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device and Shodex K-800P / K-804L / K- manufactured by Showa Denko Co., Ltd. as a column. 804L can be calculated by measuring the column temperature at 40 ° C. using chloroform or the like as a mobile phase and using a standard polystyrene calibration curve.

Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetphenone skeleton, novolak skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantan skeleton, and terpen. Examples thereof include phenoxy resins having one or more skeletons selected from the group consisting of skeletons and trimethylcyclohexane skeletons. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. The phenoxy resin may be used alone or in combination of two or more. Specific examples of the phenoxy resin include "1256" and "4250" (both bisphenol A skeleton-containing phenoxy resin), "YX8100" (bisphenol S skeleton-containing phenoxy resin), and "YX6954" (bisphenol acetophenone) manufactured by Mitsubishi Chemical Corporation. (Skeletal-containing phenoxy resin), and also "FX280" and "FX293" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794" manufactured by Mitsubishi Chemical Co., Ltd. , "YL7213", "YL7290", "YL7482" and the like.

Examples of the polyvinyl acetal resin include polyvinyl formal resin and polyvinyl butyral resin, and polyvinyl butyral resin is preferable. Specific examples of the polyvinyl acetal resin include "Electrified Butyral 4000-2", "Electrified Butyral 5000-A", "Electrified Butyral 6000-C", "Electrified Butyral 6000-EP", Sekisui Chemical Co., Ltd. Examples thereof include Eslek 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 "Rikacoat SN20" and "Rikacoat PN20" manufactured by New Japan Chemical Co., Ltd. Specific examples of the polyimide resin include a 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), and a polysiloxane skeleton. Examples thereof include modified polyimides such as contained polyimides (polyimides described in JP-A-2002-12667 and JP-A-2000-319386).

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

Specific examples of the polyether sulfone resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd.

Specific examples of the polysulfone resin include polysulfones "P1700" and "P3500" manufactured by Solvay Advanced Polymers Co., Ltd.

Among them, as the thermoplastic resin, a phenoxy resin and a polyvinyl acetal resin are preferable. Therefore, in one preferred embodiment, the thermoplastic resin comprises one or more selected from the group consisting of phenoxy resins and polyvinyl acetal resins.

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 further preferably 0. It is 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 phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, and the like, and phosphorus-based curing accelerators and amine-based curing accelerators. Curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators are preferable, and amine-based curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators are more preferable. The curing accelerator may be used alone or in combination of two or more.

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

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

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazole, 1,2-dimethyl imidazole, 2-ethyl-4-methyl imidazole, 1,2-dimethyl imidazole, and the like. 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 trimerite, 1-cyanoethyl- 2-Phenylimidazolium trimerite, 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecyl Imidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4- Diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline , 2-Phenylimidazoline and other imidazole compounds and adducts of the imidazole compound and an epoxy resin are mentioned, with 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole being preferred.

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

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, and trimethylguanidine. Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] deca-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadesylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 Examples thereof include −allyl biguanide, 1-phenylbiguanide, 1- (o-tolyl) biganide, and dicyandiamide, 1,5,7-triazabicyclo [4.4.0] deca-5-ene is preferable.

Examples of the metal-based curing accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organic metal complex include an organic cobalt complex such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, an organic copper complex such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Examples thereof include 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, zinc stearate and the like.

The content of the curing accelerator in the resin composition is not particularly limited, but is preferably 0.01% by mass to 3% by mass when the non-volatile components of the epoxy resin and the curing agent are 100% by 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. The flame retardant may be used alone or in combination of two or more.

As the flame retardant, a commercially available product may be used, and examples thereof include "HCA-HQ" manufactured by Sanko Co., Ltd. and "PX-200" manufactured by Daihachi Chemical Industry Co., Ltd. As the flame retardant, one that is hard to hydrolyze is 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, still more preferably. More preferably, it is 0.5% by mass to 10% by mass.

<(H) Organic filler>
In one embodiment, the resin composition of the present invention may contain (H) an organic filler. By containing 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 when 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 Aica Kogyo Co., Ltd.

As the rubber particles, for example, "AC3816N" and "AC3401N" manufactured by Aica Kogyo Co., Ltd. are preferable from the viewpoint that the ionicity is low and the 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 further preferably 0. It is 3% by mass to 5% by mass, or 0.5% by mass to 3% by mass.

<(I) Arbitrary additive>
In one embodiment, the resin composition of the present invention may further contain other additives, if necessary, and such other additives include, for example, an organocopper compound, an organozinc compound and an organic compound. Examples thereof include organometallic compounds such as cobalt compounds, and resin additives such as thickeners, defoaming agents, leveling agents, adhesion imparting agents, and colorants.

<Physical properties of resin composition>
When the resin composition of the present invention was heat-cured at 100 ° C. for 30 minutes and further at 180 ° C. for 30 minutes to obtain a cured product, the contact angle of the cured product surface with water before roughening the surface of the cured product was determined. When X (°) is set and the contact angle of the cured product surface with water after the surface of the cured product is roughened is Y (°), XY ≦ 0 °, preferably XY ≦ −. 3 °, more preferably XY ≦ −5 °. The lower limit of XY is not particularly limited, but is preferably −50 ° or higher, more preferably −40 ° or higher, and further preferably −30 ° or higher. By setting XY ≦ 0 °, the thin film insulation property is improved. XY can be measured according to the method described in <Measurement of contact angle> described later.

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

When the resin composition of the present invention was thermally cured at 100 ° C. for 30 minutes and further at 180 ° C. for 30 minutes to obtain a cured product, the contact angle of the cured product surface with water before the surface of the cured product was roughened. 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 becomes good. The contact angle X can be measured according to the method described in <Measurement of contact angle> described later.

The procedure for roughening treatment when measuring the contact angle can be performed according to the method described in <Measurement of contact angle> described later. Specifically, it is immersed in a predetermined swelling solution at 60 ° C. for 5 minutes, then in a predetermined oxidizing agent solution at 80 ° C. for 10 minutes, and finally 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, still more preferably 8 μm or less, from the viewpoint of reducing the thickness of the printed wiring board. The lower limit of the thickness of the resin composition layer is not particularly limited, but may be usually 1 μm or more, 1.5 μm or more, 2 μm or more, or the like.

Examples of the support include a film made of a plastic material, a metal foil, and a paper pattern, 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, the plastic material may be, for example, polyethylene terephthalate (hereinafter abbreviated as "PET") or polyethylene naphthalate (hereinafter abbreviated as "PEN"). ) And other polyesters, polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethylmethacrylate (PMMA), cyclic polyolefins, triacetylcellulose (TAC), polyethersulfide (PES), polyethers. Examples thereof include ketones and polyethylene. Of these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil, and 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.) may be used. You may use it.

The surface of the support to be joined to the resin composition layer may be subjected to a matte treatment, a corona treatment, or an antistatic treatment.

Further, as the support, a support with a release layer having a release layer on the surface to be joined with the resin composition layer may be used. Examples of the release agent used for the release layer of the support with the release layer include one or more release agents selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. .. As the support with a release layer, a commercially available product may be used. For example, "SK-1" and "SK-1" manufactured by Lintec Corporation, which are PET films having a release layer containing an alkyd resin-based release agent as a main component. Examples include "AL-5" and "AL-7", "Lumilar T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Corporation, and "Unipee" manufactured by Unitika.

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

For the resin sheet, for example, a resin varnish in which a resin composition is dissolved in an organic solvent is prepared, and this resin varnish is applied onto a support using a die coater or the like and further dried to form a resin composition layer. It can be manufactured by.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone, acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, cellosolve and butyl carbitol and the like. Carbitols, aromatic hydrocarbons such as toluene and xylene, and amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone can be mentioned. The organic solvent may be used alone or in combination of two or more.

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

In the resin sheet, a protective film similar 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). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to prevent dust and the like from adhering to the surface of the resin composition layer and scratches. The resin sheet can be rolled up and stored. When the resin sheet has a protective film, it can be used by peeling off the protective film.

The resin sheet of the present invention provides an insulating layer (cured product of the resin composition layer) having excellent thin film insulating properties. 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. It can be more preferably used as a resin sheet (resin sheet for an interlayer insulating layer of a printed wiring board). Further, for example, in a printed wiring board provided with 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 from the sheet, the thickness of the insulating layer between the first and second conductor layers is set to 6 μm or less (preferably 5.5 μm or less, more preferably 5 μm or less), and the insulation performance is excellent. be able to.

The insulating layer formed by using the resin sheet (or resin composition) of the present invention exhibits good plating adhesion. That is, it provides an insulating layer showing good plating peel strength. The plating peel strength is preferably 1.5 kgf / cm or less, more preferably 1 kgf / cm or less, and further 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 performed according to the method described later (Measurement of plating adhesion (plating peel strength)).

The insulating layer formed by using the resin sheet (or resin composition) of the present invention shows good results in the insulation resistance value after 200 hours in an environment where 130 ° C., 85 RH%, and 3.3 V is applied. That is, it provides an insulating layer showing a good insulation resistance value. 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. No particular limitation is imposed on the lower limit is preferably 10 ⁷ Omega or more, more preferably 10 ⁸ Omega more. The insulation resistance value can be measured according to the method described in <Evaluation of insulation reliability of the insulating layer> described later.

[Manufacturing method of printed wiring board and printed wiring board]
The printed wiring board of the present invention includes an insulating layer, a first conductor layer, and a second conductor layer formed by 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 called a wiring layer). .. Since the insulating layer formed by the cured product of the resin composition of the present invention is excellent in thin film insulating property, it is excellent in insulating property 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, still 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 by an example in FIG. It refers to the thickness t1 of the layer 7. The first and second conductor layers are adjacent conductor layers via an insulating layer, 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 <Measuring the thickness of the insulating layer between the conductor layers> described later.

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

The printed wiring board of the present invention can be manufactured by a method including the following steps (I) and (II) using the above-mentioned resin sheet.
(I) A step of laminating the resin composition layer of the resin sheet on the inner layer substrate so as to be bonded to the inner layer substrate (II) A step of thermosetting the resin composition layer to form an insulating layer.

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

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

The inner layer substrate and the resin sheet may be laminated by a vacuum laminating method. In the vacuum laminating method, the heat crimping temperature is preferably in the range of 60 ° C. to 160 ° C., more preferably 80 ° C. to 140 ° C., and the heat crimping pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. It is in the range of .29 MPa to 1.47 MPa, and the heat crimping time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions at a pressure of 26.7 hPa or less.

Lamination can be performed by a commercially available vacuum laminator. Examples of commercially available vacuum laminators include vacuum pressurizing laminators manufactured by Meiki Co., Ltd., vacuum applicators manufactured by Nikko Materials, and the like.

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

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

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

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

For example, the thermosetting conditions of the resin composition layer differ depending on the type of the resin composition and the like, but 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 170 ° C. to 170 ° C. 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).

The resin composition layer may be preheated at a temperature lower than the curing temperature before the resin composition layer is thermally cured. For example, prior to thermosetting the resin composition layer, the resin composition layer is heated 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 longer (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

In manufacturing the printed wiring board, (III) a step of drilling a hole in the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer may be further carried out. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art used for manufacturing a printed wiring board. When the support is removed after the step (II), the removal of the support is performed between the steps (II) and the step (III), between the steps (III) and the step (IV), or the step ( It may be carried out between IV) and step (V). Further, if necessary, the formation of the insulating layer and the conductor layer in steps (II) to (V) may be repeated to form a multilayer wiring board. In this case, the thickness of the insulating layer between the respective conductor layers (t1 in FIG. 1) is preferably within the above range.

The step (III) is a step of drilling holes in the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. The step (III) may be carried out by using, for example, a drill, a laser, a plasma, or the like, depending on the composition of the resin composition used for forming the insulating layer. The size and shape of the hole 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 of the roughening treatment are not particularly limited, and known procedures and conditions usually used when forming the insulating layer of the printed wiring board can be adopted. 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. The swelling solution is not particularly limited, and examples thereof include an alkaline solution and a surfactant solution, and an alkaline solution is preferable, and the alkaline solution is more preferably a sodium hydroxide solution and a potassium hydroxide solution. Examples of commercially available swelling liquids include "Swelling Dip Security SBU" and "Swelling Dip Security SBU" manufactured by Atotech Japan. The swelling treatment with the swelling liquid is not particularly limited, but can be performed, for example, by immersing the insulating layer in the swelling liquid at 30 ° C. to 90 ° C. for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40 ° C. to 80 ° C. for 5 minutes to 15 minutes. The oxidizing agent is not particularly limited, and examples thereof include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated to 60 ° C. 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 oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Security P" manufactured by Atotech Japan. Further, the neutralizing solution is preferably an acidic aqueous solution, and examples of commercially available products include "Reduction Solution Securigant P" manufactured by Atotech Japan. The treatment with the neutralizing solution can be performed by immersing the treated surface that has been roughened with an oxidizing agent in the neutralizing solution at 30 ° C. to 80 ° C. for 5 to 30 minutes. From the viewpoint of workability and the like, a method of immersing the object roughened with an oxidizing agent in a neutralizing solution at 40 ° C. to 70 ° C. for 5 to 20 minutes is preferable.

In one embodiment, the arithmetic mean 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, still more preferably 300 nm or less. The lower limit is not particularly limited, but is preferably 0.5 nm or more, more preferably 1 nm or more. The root mean square roughness Rq of the surface of the insulating layer after the roughening treatment is preferably 400 nm or less, more preferably 350 nm or less, and further preferably 300 nm or less. The lower limit is not particularly limited, but is preferably 0.5 nm or more, more preferably 1 nm or more. The arithmetic mean roughness (Ra) and root mean square roughness (Rq) of the insulating layer surface can be measured using a non-contact surface roughness meter, and the details will be described later (arithmetic mean 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, and when the conductor layer is formed on the inner layer substrate, the conductor layer is the first conductor layer. The 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, and the alloy layer may be, for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper, etc.). A layer formed from a nickel alloy and a copper / titanium alloy) can be mentioned. Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy, copper, etc. An alloy layer of a nickel alloy or a copper-titanium alloy is preferable, and a monometal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of a nickel-chromium alloy is more preferable, and a single copper is preferable. A metal layer is more preferred.

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

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

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 of forming the conductor layer by the semi-additive method will be shown.

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer to expose a part of the plating seed layer corresponding to a desired wiring pattern. After forming a metal layer by electrolytic plating on the exposed plating seed layer, the mask pattern is removed. After that, the 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 good component embedding properties, it can be suitably used even when the printed wiring board is a component-embedded circuit board. The component-embedded circuit board can be manufactured by a known manufacturing method.

The printed wiring board manufactured by using the resin sheet of the present invention includes an insulating layer which 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 by using the printed wiring board of the present invention.

Examples of semiconductor devices include various semiconductor devices used in electric products (for example, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (for example, motorcycles, automobiles, trains, ships, aircraft, etc.).

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 point" is a "place for transmitting an electric signal in the printed wiring board", and the place may be a surface or an embedded place. Further, the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

The method for mounting a semiconductor chip in 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 thereof 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, the "mounting method using the bumpless build-up layer (BBUL)" means "a mounting method in which the semiconductor chip is directly embedded in the recess of the printed wiring board and the semiconductor chip is connected to the wiring on the printed wiring board". Is.

Hereinafter, the present invention will be specifically described with reference to Examples. The present invention is not limited to these examples. In the following, "parts" and "%" mean "parts 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 Co., Ltd.), and 10 g of methyl ethyl ketone were weighed in a vial and dispersed by ultrasonic waves 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 based on the median diameter was calculated.

<Measurement of specific surface area of inorganic filler>
The specific surface area of the inorganic filler was measured using a BET fully automatic specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech).

<Inorganic filler used>
Inorganic filler 1: Spherical silica (“SPH516-05” manufactured by Nippon Steel & Sumitomo Metal Materials, average particle size 0.29 μm, specific surface area 16.3 m ² / g) per 100 parts, 3,3,3-trifluoro Surface-treated with 1 part of propyltrimethoxysilane (KBM-7103, manufactured by Shinetsu Chemical Industry Co., Ltd.).
Inorganic filler 2: N-phenyl-3-aminopropyl for 100 parts of spherical silica (“SPH516-05” manufactured by Nippon Steel & Sumitomo Metal Materials, 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 Industry Co., Ltd.).
Inorganic filler 3: 3,3,3-trifluoro per 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 (KBM-7103, manufactured by Shinetsu Chemical Industry Co., Ltd.).
Inorganic filler 4: N-phenyl-3-aminopropyltri for 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 Industry Co., Ltd.).
Inorganic filler 5: Spherical silica (“SC1500SQ” manufactured by Admatex (“SO-C1” surface-treated with hexamethyldisilazane), average particle size 0.63 μm, specific surface area 11.2 m ² / g) 100 parts On the other hand, surface-treated with 1 part of N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM573).

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

<Preparation of resin composition 2>
6 parts of bixilenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent of about 185), 10 parts of naphthalene type epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 332), bisphenol AF type epoxy resin ( Mitsubishi Chemical Co., Ltd. "YL7760", epoxy equivalent about 238) 10 parts, bisphenol type epoxy resin (Nittetsu Sumikin Chemical Co., Ltd. "ZX1059", epoxy equivalent about 169, bisphenol A type and bisphenol F type 1: 1 mixture) 4 2 parts of a phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Co., Ltd., a 1: 1 solution of cyclohexanone: methyl ethyl ketone (MEK) having a solid content of 30% by mass) with 20 parts of solvent naphtha and 10 parts of cyclohexanone while stirring. It was melted 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 having a solid content of 50%), an active ester system. Hardener ("EXB-8000L-65M" manufactured by DIC, active group equivalent about 220, MEK solution of 65% by mass of non-volatile component) 7 parts, inorganic filler 2 90 parts, amine-based curing accelerator (4-dimethylamino) 0.05 parts of pyridine (DMAP)) was mixed, uniformly dispersed with a high-speed rotary mixer, and then filtered with a cartridge filter (“SHP020” manufactured by ROKICHNO) to prepare a resin composition 2.

<Preparation of resin composition 3>
6 parts of bixilenol 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., epoxy equivalent of about 332), naphthylene ether type epoxy resin ("EXA-7311-G4" manufactured by DIC, epoxy equivalent of about 213) 2 parts 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 cresol novolac-based curing agent containing a triazine skeleton (“LA3018-50P” manufactured by DIC, hydroxyl group equivalent of about 151, 2-methoxypropanol solution having a solid content of 50%), an active ester system. 7 parts of curing agent ("EXB-8000L-65M" manufactured by DIC, MEK solution having active group equivalent of about 220, 65% by mass of non-volatile component), 50 parts of inorganic filler 3, imidazole-based curing accelerator (1B2PZ, 1- 0.05 parts of benzyl-2-phenylimidazole) was mixed, uniformly dispersed with a high-speed rotary mixer, and then filtered with a cartridge filter (“SHP020” manufactured by ROKITECHNO) to prepare a resin composition 3.

<Preparation of resin composition 4>
6 parts of bixilenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent of about 185), 10 parts of naphthalene type epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 332), bisphenol AF type epoxy resin ( Mitsubishi Chemical Co., Ltd. "YL7760", epoxy equivalent about 238) 10 parts, naphthylene ether type epoxy resin (DIC Co., Ltd. "EXA-7311-G4", epoxy equivalent about 213) 2 parts, solvent naphtha 20 parts and cyclohexanone 10 It was dissolved by heating in the mixed solvent of the part 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 having a solid content of 50%), an active ester system. 7 parts of curing agent ("EXB-8000L-65M" manufactured by DIC, MEK solution having active group equivalent of about 220, 65% by mass of non-volatile component), 50 parts of inorganic filler 4, amine-based curing accelerator (4-dimethylamino) 0.05 parts of pyridine (DMAP)) was mixed, uniformly dispersed with a high-speed rotary mixer, and then filtered with a cartridge filter (“SHP020” manufactured by ROKICHNO) to prepare a resin composition 4.

<Preparation of resin composition 5>
6 parts of bixilenol 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., epoxy equivalent of about 332), cyclohexanone type epoxy resin (Mitsubishi) "ZX1658GS" manufactured by Kagaku Co., Ltd., 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 are 3 parts of a triazine skeleton-containing novolak curing agent (“LA7054” manufactured by DIC, MEK solution having a hydroxyl equivalent of about 125 and a solid content of 60%), and a naphthol curing agent (“LA7054” manufactured by DIC). SN-495V ”, hydroxyl equivalent about 231) 6 parts, inorganic filler 5 80 parts, amine-based curing accelerator (4-dimethylaminopyridine (DMAP)) 0.05 parts mixed, and uniformly with a high-speed rotation mixer. After 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 bixilenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent of about 185), 20 parts of naphthalene type epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 332), naphthylene ether type epoxy resin ("EXA-7311-G4" manufactured by DIC, epoxy equivalent about 213) 2 parts, phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Co., Ltd., cyclohexanone with a solid content of 30% by mass: 1: 1 solution of methyl ethyl ketone (MEK)) 2 The parts 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, 4 parts of a cresol novolac-based curing agent containing a triazine skeleton (“LA3018-50P” manufactured by DIC, hydroxyl group equivalent of about 151, 2-methoxypropanol solution having a solid content of 50%), an active ester system 7 parts of curing agent ("EXB-8000L-65M" manufactured by DIC, MEK solution having active group equivalent of about 220, 65% by mass of non-volatile component), 80 parts of inorganic filler 5, imidazole-based curing accelerator (1B2PZ, 1- 0.05 parts of benzyl-2-phenylimidazole) was mixed, uniformly dispersed with a high-speed rotary mixer, and then filtered with a cartridge filter (“SHP020” manufactured by ROKITECHNO) to prepare a resin composition 6.

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

[Preparation of resin sheet]
As a support, a PET film ("Lumilar R80" manufactured by Toray Industries, Inc., thickness 38 μm, softening point 130 ° C., "Release PET") treated with an alkyd resin-based mold release agent ("AL-5" manufactured by Lintec Corporation). I prepared.

Each resin composition was uniformly applied on a release PET with a die coater so that the thickness of the resin composition layer after drying was 13 μm, and dried at 70 ° C. to 95 ° C. for 2 minutes to release the PET. A resin composition layer was obtained on top. Next, a rough surface of a polypropylene film (“Alfan 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 that is not bonded to the support of the resin sheet. Laminated in. As a result, a resin sheet composed of a release PET (support), a resin composition layer, and a protective film was obtained.

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

(2) Laminating of resin sheets The protective film was peeled off from each resin sheet produced in Examples and Comparative Examples, and a batch type vacuum pressure laminator (2-stage build-up laminator manufactured by Nikko Materials Co., Ltd., CVP700) was used. Both sides of the inner layer circuit board were laminated so that the resin composition layer was in contact with the inner layer circuit board. Lamination was carried out by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and crimping at 130 ° C. and a pressure of 0.74 MPa for 45 seconds. Then, heat 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 thermoset for 30 minutes after being placed in an oven at 100 ° C., and then transferred to an oven at 180 ° C. for 30 minutes to increase the thickness. An insulating layer of 5 μm was formed, and the release PET was peeled off. This is referred to as "evaluation substrate A".

(4) Step of Roughening Treatment The evaluation substrate A on which the insulating layer was formed was subjected to desmear treatment as a roughening treatment. As the desmear treatment, the following wet desmear treatment was carried out.

Wet desmear treatment:
In a swollen solution (Atotech Japan's "Swelling Dip Securigant P", an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60 ° C. for 5 minutes, then an oxidizing agent solution (Atotech Japan's "Concentrate Compact CP" , Aqueous solution of potassium permanganate concentration of about 6%, sodium hydroxide concentration of about 4%) at 80 ° C. for 10 minutes, and finally in a neutralizing solution (Atotech Japan's "Reduction Solution Securigant P", aqueous sulfuric acid solution) After soaking 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 a chemical solution manufactured by Atotech Japan). The conductor layer was formed by performing the copper plating step).

1. 1. Alkaline cleaning (cleaning of the surface of the insulating layer with via holes and charge adjustment)
Product name: Cleaning was performed at 60 ° C. for 5 minutes using Cleaning Cleaner Security 902 (trade name).
2. Soft etching (cleaning inside the via hole)
Treatment was carried out at 30 ° C. for 1 minute using an aqueous sodium sulfate-acidic peroxodisulfate solution.
3. 3. Predip (Adjustment of charge on the surface of the insulating layer for Pd application)
Pre. Treatment was performed at room temperature for 1 minute using Dip Neoganth B (trade name).
4. Add activator (give Pd to the surface of the insulating layer)
Treatment was performed at 35 ° C. for 5 minutes using Activator Neoganth 834 (trade name).
5. Reduction (Reduction of Pd applied to the insulating layer)
Reducer Neoganth WA (trade name) and Reducer Acceralator 810 mod. Using a mixed solution with (trade name), the treatment was carried out at 30 ° C. for 5 minutes.
6. Electroless copper plating process (Cu is deposited on the surface of the insulating layer (Pd surface))
A mixture of Basic Solution Printganth MSK-DK (trade name), Copper solution Printganth MSK (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 Step Next, an electrolytic copper plating step was carried out under the condition that the via hole was filled with copper using a chemical solution manufactured by Atotech Japan. After that, as a resist pattern for patterning by etching, a land pattern having a diameter of 1 mm conducted through the via hole and a circular conductor pattern having a diameter of 10 mm not connected to the lower layer conductor were used, and the thickness of 10 μm was applied to the surface of the insulating layer. A conductor layer with lands and conductor patterns was formed. Next, the annealing treatment was performed at 200 ° C. for 90 minutes. This substrate was designated as "evaluation substrate B".

(Measurement of Arithmetic Mean Roughness (Ra), Root Mean Square Roughness (Rq))
The surface of the insulating layer outside the circular conductor pattern of the evaluation substrate B was obtained by using a non-contact type surface roughness meter (WYKO NT3300 manufactured by Becoin Sturments) in VSI contact mode and a 50x lens with a measurement range of 121 μm × 92 μm. The Ra value and the Rq value were obtained from the numerical values obtained. The average value of each of the 6 points was calculated, and the results of rounding off the last digit are shown in the table below.

(Measurement of plating adhesion (plating peel strength))
Make a notch in the conductor layer of the evaluation substrate B with a width of 10 mm and a length of 100 mm, peel off one end of the notch, and use a gripper (manufactured by TSE, Autocom type tester AC-50C-SL). The load (kgf / cm) when 35 mm was peeled off in the vertical direction at a speed of 50 mm / min at room temperature was measured using a grasping and Instron universal tester to determine the peel strength.

<Measurement of the thickness of the insulating layer between conductor layers>
A cross section of the evaluation substrate B was observed using a FIB-SEM composite device (“SMI3050SE” manufactured by SII Nanotechnology Co., Ltd.). Specifically, a cross section in a direction perpendicular to the surface of the conductor layer was cut out by a FIB (focused ion beam), and the thickness of the insulating layer between the conductor layers was measured from the cross section SEM image. For each sample, five randomly selected cross-sectional SEM images were observed, and the average value was taken as the thickness (μm) of the insulating layer between the conductor layers and shown in the table below.

<Evaluation of insulation reliability of insulation layer>
An advanced accelerated life test device (with the circular conductor side of the evaluation substrate B obtained above having a diameter of 10 mm as a + electrode and the lattice conductor (copper) side of the inner layer circuit board connected to the land having a diameter of 1 mm as a-electrode). Using ETAC's "PM422"), the insulation resistance value when 200 hours have passed under the conditions of 130 ° C., 85% relative humidity, and 3.3V DC voltage applied is determined by the electrochemical migration tester (manufactured by J-RAS). It was measured by "ECM-100"). The measurement was carried out 6 times, "○" and when the resistance value is not less than 10 ⁷ Omega in all test pieces of 6 points, if less than even one 10 ⁷ Omega is a "×", the evaluation result and the insulation resistance Is shown in the table below. The insulation resistance values shown in the table below are the minimum insulation resistance values of the six test pieces.

<Measurement of contact angle>
The contact angle of water droplets on the surface of the cured product by the sessile drop 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 prepare 1.0 μL of water droplets, which were adhered to the surface of the insulating layer of the evaluation substrate A. The contact angle 2000 ms after the water droplet was attached was measured with the above-mentioned automatic contact angle meter and defined as X (°).

Next, the roughening treatment of the insulating layer in the evaluation substrate A was performed by the same method as the step of performing the roughening treatment in (4) above. Then, pure water was filled in a syringe to prepare 1.0 μL of water droplets, which were adhered to the surface of the roughened insulating layer of the evaluation substrate A. The contact angle 2000 ms after the water droplets were attached was measured with the above-mentioned automatic contact angle meter and defined as Y (°). When XY is 0 or less, it is evaluated as “◯”, and when XY exceeds 0, it is evaluated as “x”. Further, the case where Y is 80 ° or more is designated as “◯”, and the case where Y is less than 80 ° is designated as “x”.

5 First conductor layer 51 Main surface of the first conductor layer 6 Second conductor layer 61 Main surface of the second conductor layer 7 Insulation layer

Claims (11)

A support and a resin composition layer formed in the tree fat composition provided on the support seen including,
The resin composition contains (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler.
The content of the component (C) is 50% by mass or more when the non-volatile component in the resin composition is 100% by mass.
When the resin composition was heat-cured at 100 ° C. for 30 minutes and further at 180 ° C. for 30 minutes to obtain a cured product, the contact angle of the cured product surface with water before roughening the surface of the cured product was set to X (°). ), And when the contact angle of the cured product surface with water after roughening the cured product surface is Y (°),
A resin sheet satisfying the relationship of XY ≦ 0 °, Y ≧ 80 °, and X <80 ° . The resin sheet according to claim 1, wherein the average particle size of the component (C) is 0.05 μm to 0.35 μm. The resin sheet according to claim 1 or 2, which contains a fluorine compound. The resin sheet according to claim 3, wherein the fluorine compound is a fluorine-containing epoxy resin. The resin sheet according to claim 3 or 4, wherein the fluorine compound is (D) a fluorine-containing silane coupling agent. The resin sheet according to claim 5, wherein the component (C) is surface-treated with the component (D). The resin sheet according to any one of claims 1 to 6, which is used for forming an insulating layer of a printed wiring board. The resin sheet according to any one of claims 1 to 7 , wherein the thickness of the resin composition layer is 15 μm or less. The insulation of 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 any one of claims 1 to 8 , which is used for layer formation. A printed wiring board comprising 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.
Insulating layer, Ri cured der tree fat composition,
The resin composition contains (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler.
The content of the component (C) is 50% by mass or more when the non-volatile component in the resin composition is 100% by mass.
When the resin composition was heat-cured at 100 ° C. for 30 minutes and further at 180 ° C. for 30 minutes to obtain a cured product, the contact angle of the cured product surface with water before roughening the surface of the cured product was set to X (°). ), And when the contact angle of the cured product surface with water after roughening the cured product surface is Y (°),
A printed wiring board that satisfies the relationship of XY ≦ 0 °, Y ≧ 80 °, and X <80 ° . It includes a printed wiring board according to claim 1 0, semiconductor device.

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