JP6911311B2 - 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, further thinning of printed wiring boards has been promoted, and the thickness of the inner layer substrate and the insulating layer tends to be further reduced. For example, Patent Document 1 describes a resin composition for a thin film that can be made thinner.

Japanese Unexamined Patent Publication No. 2014-152309

In Patent Document 1, when a thin film is applied to an insulating layer, the present inventors tend to increase the roughness and decrease the peel strength (sometimes referred to as plating peel strength or peel strength) from plating. We have found that there is, and in order to solve these problems, we are proposing to set the blending amount of the thermoplastic resin to a predetermined amount. However, in this document, the insulation performance when the thickness of the insulating layer is reduced (hereinafter, may be referred to as "thin film insulating property") is not studied at all.

When the insulating layer is thin, 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. It becomes more difficult to maintain the insulation performance than the conventional one. In particular, when the insulating layer formed between conductor layers such as wiring is thin, the surface of the insulating layer tends to be roughened, and the insulation reliability tends to be unstable. Further, the insulation performance of the insulating layer differs between the portion with wiring and the portion without wiring, and the insulation reliability tends to be unstable.

An object of the present invention is a resin composition capable of imparting an insulating layer having excellent thin film insulating properties and peel strength even if it is thin; a resin sheet containing the resin composition; insulation formed by using the resin composition. It is an object of the present invention to provide a printed wiring board provided with a layer and a semiconductor device.

As described above, the present inventors have found that when the thin film is applied to the insulating layer, the roughness tends to increase and the peel strength tends to decrease. As a result of diligent studies to solve the above problems, the present inventors roughened the cured products of the resin compositions having a thickness of about 5 μm and about 10 μm, respectively, and roughened the roughened surface with an arithmetic mean roughness Ra. By adjusting each component contained in the resin composition so that the ten-point average roughness Rz satisfies a predetermined relationship, that is, the following formulas (1) and (2) are satisfied, even if it is thin, it is a thin film. We have found that it is possible to provide an insulating layer having excellent insulating properties and peel strength, and have completed the present invention.

That is, the present invention includes the following contents.
[1] A resin composition for forming an insulating layer provided between a first conductor layer and a second conductor layer.
The surface of the first layer having a thickness of 5.0 ± 0.8 μm, which comprises a cured product obtained by thermally curing the resin composition at 100 ° C. for 30 minutes and further at 180 ° C. for 30 minutes, was added to a swelling solution at 60 ° C. Arithmetic mean roughness Ra (5) and ten-point average roughness Rz of the surface of the first layer after immersing in an oxidizing agent solution at 80 ° C. for 10 minutes and in a neutralizing solution at 40 ° C. for 5 minutes. (5), and
The surface of the second layer having a thickness of 10.0 ± 0.8 μm, which comprises a cured product obtained by thermosetting the resin composition at 100 ° C. for 30 minutes and further at 180 ° C. for 30 minutes, was added to a swelling solution at 60 ° C. Arithmetic mean roughness Ra (10) and ten-point average roughness Rz on the surface of the second layer after immersing in an oxidizing agent solution at 80 ° C. for 10 minutes and in a neutralizing solution at 40 ° C. for 5 minutes. (10) is
1 ≤ Ra (5) / Ra (10) ≤ 1.2 (1)
1 ≦ Rz (5) / Rz (10) ≦ 1.4 (2)
A resin composition that satisfies the relationship of.
[2] The resin composition according to [1], which contains an inorganic filler.
[3] The resin composition according to [2], wherein the content of the inorganic filler 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 inorganic filler 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 any one of [1] to [6], which is used for forming an insulating layer of a printed wiring board.
[8] The thickness of the resin composition layer includes the support and the resin composition layer provided on the support and formed of the resin composition according to any one of [1] to [7]. A resin sheet having a thickness of 15 μm or less.
[9] The resin sheet according to [8], wherein the thickness of the resin composition layer is 10 μm or less.
[10] The first conductor layer and the second conductor layer include a first conductor layer, a second conductor layer, and an insulating layer formed between the first conductor layer and the second conductor layer. The resin sheet according to [8] or [9], which is used for forming the insulating layer of a printed wiring board having a distance from the conductor layer of 6 μm or less.
[11] Includes a first conductor layer, a second conductor layer, and an insulating layer formed between the first conductor layer and the second conductor layer.
A printed wiring board in which the distance between the first conductor layer and the second conductor layer is 6 μm or less.
The insulating layer is a printed wiring board which is a cured product of the resin composition according to any one of [1] to [7].
[12] A semiconductor device including the printed wiring board according to [11].

According to the present invention, a resin composition capable of imparting an insulating layer having excellent thin film insulating properties and peel strength even if it is thin; a resin sheet containing the resin composition; insulation formed by using the resin composition. A printed wiring board having a layer 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.

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.

[Resin composition]
The resin composition of the present invention is a resin composition for forming an insulating layer provided between the first conductor layer and the second conductor layer, and the resin composition is further added at 100 ° C. for 30 minutes. The surface of the first layer having a thickness of 5.0 ± 0.8 μm composed of a cured product obtained by heat-curing at 180 ° C. for 30 minutes was placed in a swelling solution at 60 ° C. for 5 minutes and in an oxidizing agent solution at 80 ° C. for 10 minutes. After immersing the surface of the first layer in a neutralizing solution for 5 minutes at 40 ° C. for 5 minutes, the arithmetic average roughness Ra (5) and the ten-point average roughness Rz (5) of the surface of the first layer, and the resin composition were 100. The surface of the second layer having a thickness of 10.0 ± 0.8 μm, which is made of a cured product obtained by heat-curing at ° C. for 30 minutes and further at 180 ° C. for 30 minutes, is placed in a swelling solution at 60 ° C. for 5 minutes as an oxidizing agent. The arithmetic average roughness Ra (10) and the ten-point average roughness Rz (10) of the surface of the second layer after being immersed in the solution at 80 ° C. for 10 minutes and in the neutralizing solution at 40 ° C. for 5 minutes are determined.
1 ≤ Ra (5) / Ra (10) ≤ 1.2 (1)
1 ≦ Rz (5) / Rz (10) ≦ 1.4 (2)
Satisfy the relationship. This makes it possible to provide an insulating layer having excellent thin film insulating properties and peel strength even if it is thin.
Hereinafter, the roughening treatment test is carried out by immersing the surfaces of the first layer and the second layer in the swelling solution at 60 ° C. for 5 minutes, in the oxidizing agent solution at 80 ° C. for 10 minutes, and in the neutralizing solution at 40 ° C. for 5 minutes. There is that.

Such a resin composition can be realized by adjusting each component contained in the resin composition so as to satisfy the formulas (1) and (2). Examples of the components contained in the resin composition include a composition containing a curable resin and a curing agent thereof. As the curable resin, any curable resin used when forming the insulating layer of the printed wiring board can be used, and among them, the epoxy resin is preferable. Therefore, in one embodiment, the resin composition comprises (A) an epoxy resin and (B) a curing agent. The resin composition further contains additives such as (C) inorganic filler, (D) thermoplastic resin, (E) curing accelerator, (F) flame retardant and (G) organic filler, if necessary. You may be. Further, the resin composition of the present invention preferably contains a fluorine compound from the viewpoint of satisfying the above formulas (1) and (2). 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 (G), and the fluorine compound is preferably contained as the component (A). 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. By using a fluorine compound, the surface roughness can be stably formed even if the insulating layer is thin. Hereinafter, each component contained in the resin composition of the present invention will be described in detail.

<(A) Epoxy resin>
Examples of the 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; bixyleneol. Type epoxy resin; dicyclopentadiene 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 Resins; spiro ring-containing epoxy resins; cyclohexanedimethanol type epoxy resins; naphthylene ether type epoxy resins; trimethylol type epoxy resins; tetraphenylethane type epoxy resins and the like can be mentioned. The epoxy resin may be used alone or in combination of two or more.

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. An alicyclic epoxy resin, a cyclohexanedimethanol type epoxy resin, a glycidylamine type epoxy resin, and an epoxy resin having a butadiene structure are preferable, and a glycidylamine type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a bisphenol AF Type epoxy resin and naphthalene type epoxy resin are more preferable. Specific examples of the liquid epoxy resin include "HP4032", "HP4032D" and "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), "630", "630LSD" (glycidylamine type epoxy resin), "ZX1059" (bisphenol A) manufactured by Nippon Steel & Sumitomo Metal Corporation. (Mixed product of type epoxy resin and bisphenol F type epoxy resin), "YD-8125G" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. (bisphenol A type epoxy resin), "EX-721" manufactured by Nagase Chemtex Co., Ltd. (glycidyl ester type epoxy resin) , "Selokiside 2021P" (alicyclic epoxy resin having an ester skeleton), "PB-3600" (epoxy resin having a butadiene structure) manufactured by Daicel Co., Ltd., "ZX1658", "ZX1658GS" manufactured by Nippon Steel Chemical Co., Ltd. ( Liquid 1,4-glycidylcyclohexane), "630LSD" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "E-7432", "E-7632" (perfluoroalkyl type epoxy resin) manufactured by Daikin Industries, Ltd., etc. Can be mentioned. 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), "YL7760" (bisphenol AF type epoxy resin) and the like.

The component (A) is preferably a fluorine-containing epoxy resin, which is a fluorine compound, from the viewpoint of satisfying the above formulas (1) and (2).

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 1:10 in terms of mass ratio. Is more preferable, and the range of 1: 0.5 to 1: 3 is even more preferable.

The content of the epoxy resin in the resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% 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.

The resin composition of the present invention, the fluorine-containing epoxy resin and may include a combination of fluorine-containing epoxy resin other than the epoxy resin, the mass of the fluorine-containing epoxy resin in the resin composition W _{A fluorine-containing} epoxy resin composition when the mass of the epoxy resin other than the resin was _{W B,} it is preferable that the W B / _{W a} 1 to 10, more preferably from 1 to 5, 1 to 3, or 1 to 2 Is even more preferable. By W B _/ W _A is preferably within the above range can increase the thin film insulation and peel strength of the insulating layer effectively.

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.

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 Kayaku 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, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-. Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenol, trihydroxybenzophenol, 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 the active ester-based curing agent 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 Co., Ltd.), "YLH1030" (manufactured by Mitsubishi Chemical Co., Ltd.), "YLH1048" (manufactured by Mitsubishi Chemical Co., Ltd.) and the like.

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

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 a 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 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 1:10, more preferably 1: 0.5 to 1: 3) 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 phenol-based curing agents, naphthol-based curing agents, and active ester-based curing agents).

The content of the curing agent in the resin composition is not particularly limited, but is preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 10% 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 , Zirconium oxide, barium titanate, barium titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate 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 surface roughness can be stably formed even if the insulating layer is thin.

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.

From the viewpoint of enhancing moisture resistance and dispersibility, the inorganic filler is a fluorine-containing silane coupling agent, an aminosilane-based coupling agent, an epoxysilane-based coupling agent, a mercaptosilane-based coupling agent, and a silane-based cup. It is preferably treated with one or more surface treatment agents such as a ring agent, an organosilazane compound, and a titanate-based coupling agent, and particularly preferably treated with a fluorine-containing silane coupling agent. 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., "KBM-" manufactured by Shin-Etsu Chemical Co., Ltd. 7103 ”(3,3,3-trifluoropropyltrimethoxysilane) 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 100 parts by mass of the component (C) is surface-treated with 0.2 parts by mass to 5 parts by mass of the surface treatment agent. It is preferable that the surface is treated with 0.2 parts by mass to 3 parts by mass, and the surface is preferably treated with 0.3 parts by mass to 2 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 of the inorganic filler in the resin composition is preferably 50% by mass or more 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. It is preferably 53% by mass or more, more preferably 55% 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) Thermoplastic resin>
In one embodiment, the resin composition of the present invention may contain (D) 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 8,000 or more, more preferably 10,000 or more, still more preferably 20,000 or more, and particularly preferably 40,000 or more. The upper limit is preferably 70,000 or less, more preferably 60,000 or less. 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 using a standard polystyrene calibration curve by measuring the column temperature at 40 ° C. using chloroform or the like as a mobile phase.

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 a phenoxy resin having one or more skeletons selected from the group consisting of a skeleton and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. 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 & Sumitomo Metal Corporation, "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30" manufactured by Mitsubishi Chemical Corporation. , "YL6794", "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 "electric butyral 4000-2", "electric butyral 5000-A", "electric butyral 6000-C", "electric butyral 6000-EP", and Sekisui manufactured by Denki Kagaku Kogyo 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 Shin Nihon Rika 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 polyphenylene ether resin include oligophenylene ether styrene resin "OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Company, Ltd.

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

Among them, as the thermoplastic resin, a phenoxy resin and a polyvinyl acetal resin are preferable. Therefore, in a preferred embodiment, the thermoplastic resin comprises one or more selected from the group consisting of phenoxy resins and polyvinyl acetal resins. Among them, as the thermoplastic resin, a phenoxy resin is preferable, and a phenoxy resin having a weight average molecular weight of 40,000 or more is particularly preferable. By using a phenoxy resin having a weight average molecular weight of 40,000 or more, the surface roughness can be stably formed even if the insulating layer is thin.

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.

<(E) Curing accelerator>
In one embodiment, the resin composition of the present invention may further contain (E) 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-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 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 trimellitate, 1-cyanoethyl- 2-Phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecyl Imidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-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, trimethylguanidine, and the like. 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-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 Examples thereof include −allyl biguanide, 1-phenylbiguanide, 1- (o-tolyl) biguanide, and dicyandiamide, 1,5,7-triazabicyclo [4.4.0] deca-5-ene is preferable.

Examples of the metal-based curing accelerator include organic metal complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organic metal complex include 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.

When the resin composition contains a curing accelerator, the content of the curing accelerator is preferably 0.01% by mass to 3% by mass, more preferably 0.01% by mass to 3% by mass, and 0.01% by mass. ~ 1% by mass is more preferable.

<(F) Flame Retardant>
In one embodiment, the resin composition of the present invention may contain (F) 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 preferably 0.5% by mass to 20% by mass, more preferably 0.5% by mass to 15% by mass, and 0.5% by mass to 10% by mass. Mass% is more preferred.

<(G) Organic filler>
In one embodiment, the resin composition of the present invention may contain (G) an organic filler. By containing the component (G), 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.

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 0.3% by mass. It is more preferably ~ 5% by mass, or 0.5% by mass to 3% by mass.

<(H) 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, defoamers, leveling agents, adhesion imparting agents, and colorants.

<Physical characteristics and uses of resin composition>
The resin composition of the present invention provides an insulating layer having excellent thin film insulating properties and peel strength even if it is thin. Therefore, the resin composition of the present invention can be suitably used for forming an insulating layer provided between the first conductor layer and the second conductor layer. Specifically, the resin composition of the present invention can be suitably used as a resin composition (for forming an insulating layer of a printed wiring board) for forming an insulating layer of a printed wiring board, and the printed wiring board can be used. It can be more preferably used as a resin composition for forming an interlayer insulating layer (resin composition for an interlayer insulating layer of a printed wiring board).

The resin composition of the present invention is roughened on the surface of a first layer having a thickness of 5.0 ± 0.8 μm, which is a cured product obtained by thermally curing at 100 ° C. for 30 minutes and further at 180 ° C. for 30 minutes. After the treatment test, the arithmetic mean roughness Ra (5) and the ten-point average roughness Rz (5) of the surface of the first layer and the resin composition were applied at 100 ° C. for 30 minutes and further at 180 ° C. Arithmetic mean roughness of the surface of the second layer after performing a roughening treatment test on the surface of the second layer having a thickness of 10.0 ± 0.8 μm, which is a cured product obtained by heat-curing for 30 minutes. Ra (10) and ten-point average roughness Rz (10)
1 ≤ Ra (5) / Ra (10) ≤ 1.2 (1)
1 ≦ Rz (5) / Rz (10) ≦ 1.4 (2)
Meet. By adjusting each component contained in the resin composition so as to satisfy the formulas (1) and (2), it is possible to provide an insulating layer having excellent thin film insulating properties and peel strength even if it is thin.

Ra (5) / Ra (10) preferably satisfies the above formula (1), preferably the following formula (1-1), and more preferably the following formula (1-2). In particular, the closer the ratio Ra (5) / Ra (10) is to 1.00, the more effectively the peel strength between the insulating layer and the conductor layer obtained from the resin composition can be increased.
1 ≤ Ra (5) / Ra (10) ≤ 1.19 (1-1)
1 ≤ Ra (5) / Ra (10) ≤ 1.18 (1-2)

Rz (5) / Rz (10) preferably satisfy the above formula (2), preferably the following formula (2-1), and more preferably the following formula (2-2). In particular, the closer the ratio Rz (5) / Rz (10) is to 1.00, the more effectively the thin film insulating property of the insulating layer obtained from the resin composition can be enhanced.
1 ≦ Rz (5) / Rz (10) ≦ 1.35 (2-1)
1 ≦ Rz (5) / Rz (10) ≦ 1.30 (2-2)

The thickness of the first layer is 5.0 ± 0.8 μm, preferably 5.0 ± 0.5 μm, and more preferably 5.0 ± 0.8 μm. The thickness of the second layer is 10.0 ± 0.8 μm, preferably 10.0 ± 0.6 μm, and more preferably 10.0 ± 0.5 μm. The thickness of the first layer and the second layer means the thickness of the cured product before the roughening treatment test.

The procedure for thermosetting the resin composition and the roughening treatment test when measuring Ra (5), Rz (5), Ra (10), and Rz (10) will be described later in <Roughened substrate A and for evaluation. It can be carried out according to the method described in "(3) Thermosetting of resin composition layer" and "(4) Step of roughening treatment" of Preparation of substrate A>.

The swelling liquid used in the roughening treatment test is preferably an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide. A commercially available product may be used as the swelling liquid, and examples thereof include Swering Dip Securigant P manufactured by Atotech Japan.

The oxidizing agent solution used in the roughening treatment test is preferably an aqueous solution having a potassium permanganate concentration of about 6% and a sodium hydroxide concentration of about 4%. A commercially available product may be used as the oxidizing agent solution, and examples thereof include Concentrate Compact CP manufactured by Atotech Japan.

The neutralizing solution used in the roughening treatment test is preferably an aqueous sulfuric acid solution. A commercially available product may be used as the neutralizing solution, and examples thereof include a reduction solution Securigant P manufactured by Atotech Japan.

The arithmetic mean roughness Ra (5) of the surface of the first layer is preferably 300 nm or less, more preferably 250 nm or less, still more preferably 230 nm or less, from the viewpoint of particularly enhancing the thin film insulation property of the insulating layer. The lower limit is not particularly limited, but from the viewpoint of obtaining an insulating layer having particularly excellent peel strength, it is preferably 0 nm or more, more preferably 30 nm or more, still more preferably 50 nm or more.

The ten-point average roughness Rz (5) of the surface of the first layer is preferably 2000 nm or less, more preferably 1900 nm or less, still more preferably 1800 nm or less, from the viewpoint of particularly enhancing the thin film insulation property of the insulating layer. The lower limit is not particularly limited, but from the viewpoint of obtaining an insulating layer having particularly excellent peel strength, it is preferably 0 nm or more, more preferably 300 nm or more, and further preferably 500 nm or more.

The arithmetic mean roughness Ra (10) of the surface of the second layer is preferably 250 nm or less, more preferably 230 nm or less, still more preferably 200 nm or less, from the viewpoint of particularly enhancing the thin film insulation property of the insulating layer. The lower limit is not particularly limited, but from the viewpoint of obtaining an insulating layer having particularly excellent peel strength, it is preferably 0 nm or more, more preferably 15 nm or more, and further preferably 30 nm or more.

The ten-point average roughness Rz (10) of the surface of the second layer is preferably 2000 nm or less, more preferably 1800 nm or less, and further preferably 1700 nm or less from the viewpoint of particularly enhancing the thin film insulation property of the insulating layer. The lower limit is not particularly limited, but from the viewpoint of obtaining an insulating layer having particularly excellent peel strength, it is preferably 0 nm or more, more preferably 300 nm or more, and further preferably 500 nm or more.

The cured product obtained by thermally curing the resin composition of the present invention at 100 ° C. for 30 minutes and further at 180 ° C. for 30 minutes exhibits a characteristic of excellent peel strength with a conductor layer made of plating or the like. For details, when the resin composition of the present invention is subjected to a roughening treatment test on the surface of a cured product obtained by thermally curing at 100 ° C. for 30 minutes and further at 180 ° C. for 30 minutes, and then a conductor layer is formed. It exhibits the characteristic that the peel strength between the cured product and the conductor layer is excellent. The peel strength is preferably 0.3 kgf / cm or more, more preferably 0.4 kgf / cm or more, still more preferably 0.45 kgf / cm or more when the thickness of the insulating layer is 5 ± 0.8 μm. On the other hand, the upper limit of the peel strength is not particularly limited, but may be 1.5 kgf / cm or less, 1 kgf / cm or less, or the like. When the thickness of the insulating layer is 10 ± 0.8 μm, the peel strength is preferably 0.4 kgf / cm or more, more preferably 0.45 kgf / cm or more, still more preferably 0.5 kgf / cm or more. .. On the other hand, the upper limit of the peel strength is not particularly limited, but may be 1.5 kgf / cm or less, 1 kgf / cm or less, or the like. The peel strength can be evaluated according to the method described in <Measurement of plating adhesion (plating peel strength)> described later.

The cured product obtained by thermally curing the resin composition of the present invention at 100 ° C. for 30 minutes and further at 180 ° C. for 30 minutes exhibits excellent thin film insulation, that is, an excellent insulation resistance value. Specifically, when the surface of the cured product obtained by thermally curing the resin composition of the present invention at 100 ° C. for 30 minutes and further at 180 ° C. for 30 minutes was subjected to a roughening treatment test, the cured product was thin. However, the cured product shows a high insulation resistance value. The insulation resistance value of the cured product having a thickness of 5 ± 0.8 μm is preferably 0.1 × 10 ¹⁰ Ω or more, more preferably 0.5 × 10 ¹⁰ Ω or more, and further preferably 1 × 10 ¹⁰ Ω or more. be. On the other hand, the upper limit of the insulation resistance value of the cured product having a thickness of 5 ± 0.8 μm is not particularly limited, but may be 10 × 10 ¹² Ω or less, 100 × 10 ¹² Ω or less, or the like. The insulation resistance value of the cured product having a thickness of 10 ± 0.8 μm is preferably 0.1 × 10 ¹¹ Ω or more, more preferably 1 × 10 ¹¹ Ω or more, and further preferably 1 × 10 ¹¹ Ω or more. On the other hand, the upper limit of the insulation resistance value of the cured product having a thickness of 10 ± 0.8 μm is not particularly limited, but may be 10 × 10 ¹² Ω or less, 100 × 10 ¹² Ω or less, or the like. The insulation resistance value can be measured according to the method described in <Evaluation of insulation reliability of the insulating layer> described later.

[Resin sheet]
The resin sheet of the present invention includes a support and a resin composition layer provided on the support, the resin composition layer is formed from the resin composition of the present invention, and the thickness of the resin composition layer is 15 μm. It is as follows.

The thickness of the resin composition layer is 15 μm or less, preferably 10 μm or less, more preferably 8 μm or less, still more preferably 5 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 release paper, and a film made of a plastic material and a metal leaf 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, may be 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 polyimides. 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 support may be matted, corona-treated, or antistatic-treated on the surface to be joined to the resin composition layer.

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, acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, cellosolve and butyl carbitol and the like. Examples thereof include carbitols, aromatic hydrocarbons such as toluene and xylene, and amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. 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 and peel strength even if it is thin. 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 including a first conductor layer, a second conductor layer, and an insulating layer formed between the first conductor layer and the second conductor layer, the present invention. By forming the insulating layer from the resin sheet, the distance between the first and second conductor layers (thickness of the insulating layer between the first and second conductor layers) is 6 μm or less (preferably 5.5 μm or less, more preferably. Is 5 μm or less) and has excellent thin film insulation.

[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 a wiring layer). be). Since the insulating layer formed by the cured product of the resin composition of the present invention has excellent thin film insulating properties, the distance between the first conductor layer and the second conductor layer (the insulating layer between the first and second conductor layers). Excellent insulation even when the thickness) 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 distance between the first conductor layer and the second conductor layer (thickness of the insulating layer between the first and second conductor layers) is the main surface of the first conductor layer 1 as shown by an example in FIG. It refers to the thickness t1 of the insulating layer 3 between the main surface 21 of the 11 and the second conductor layer 2. The first and second conductor layers are adjacent conductor layers via an insulating layer, and the main surface 11 and the main surface 21 face each other. The thickness of the insulating layer between the first and second conductor layers can be measured according to the method described in <Measurement of distance between conductor layers (thickness of insulating layer between conductor layers)> described later.

The thickness t2 of the entire insulating layer is preferably 15 μm or less, more preferably 10 μm or less, still more preferably 8 μm or less, or 5 μm or less. The lower limit is not particularly limited, but is usually 1 μm or more, 1.5 μm or more, 2 μm or more, and the like.

The printed wiring board of the present invention can be produced by using the above-mentioned resin sheet by a method including the following steps (I) and (II).
(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 not to press the heat-bonded member directly onto the resin sheet, but to press it 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 a vacuum pressurizing laminator manufactured by Meiki Co., Ltd., a vacuum applicator manufactured by Nikko Materials, and a batch type vacuum pressurizing laminator.

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).

Before the resin composition layer is thermally cured, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermosetting the resin composition layer, the resin composition layer is 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 support is removed 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 dimensions and shape of the holes may be appropriately determined according to the design of the printed wiring board.

Step (IV) is a step of roughening the insulating layer. The procedure and conditions 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 used for the roughening treatment is not particularly limited, and examples thereof include an alkaline solution and a surfactant solution, preferably an alkaline solution, and the alkaline solution is more preferably a sodium hydroxide solution or a potassium hydroxide solution. preferable. 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 used in the roughening treatment 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. The neutralizing solution used for the roughening treatment 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 liquid can be carried out by immersing the treated surface that has been roughened with the oxidizing agent in the neutralizing liquid at 30 ° C. to 80 ° C. for 5 to 30 minutes. From the viewpoint of workability and the like, a method 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.

For the roughening treatment in the step (IV), the same procedure and conditions as those in the roughening treatment test may be adopted.

In one embodiment, when the thickness of the insulating layer between the first and second conductor layers is about 5 μm, the arithmetic mean roughness (Ra) of the surface of the insulating layer after the roughening treatment is preferably 300 nm or less, more preferably 300 nm or less. Is 250 nm or less, more preferably 230 nm or less. The lower limit is not particularly limited, but is preferably 0 nm or more, more preferably 30 nm or more, and further preferably 50 nm or more. When the thickness of the insulating layer between the first and second conductor layers is about 5 μm, the ten-point average roughness (Rz) of the surface of the insulating layer after the roughening treatment is preferably 2000 nm or less, more preferably 1900 nm. Below, it is more preferably 1800 nm or less. The lower limit is not particularly limited, but is preferably 0 nm or more, more preferably 300 nm or more, and further preferably 500 nm or more. The arithmetic mean roughness (Ra) and the ten-point average roughness (Rz) of the surface of the insulating layer are measured according to the method described in <Measurement of Arithmetic Mean Roughness (Ra) and Ten-Point Average Roughness (Rz)> described later. can do.

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 of 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 single metal 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 layer 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 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 that exposes a part of the plating seed layer corresponding to a desired wiring pattern is formed on the formed plating seed layer. 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.

A printed wiring board manufactured 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 electrical 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 the 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 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 Co., Ltd.).

<Inorganic filler used>
Inorganic filler 1: N-phenyl-3-aminopropyl for 100 parts of spherical silica (“SPH516-05” manufactured by Nippon Steel & Sumikin Materials Co., Ltd., average particle size 0.29 μm, specific surface area 16.3 m ^{2 / g)} Surface-treated with 1 part of trimethoxysilane (KBM573, manufactured by Shin-Etsu Chemical Industry Co., Ltd.).
Inorganic filler 2: 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 Co., Ltd.).
Inorganic filler 3: N-phenyl-3-aminopropyltrimethoxysilane (N-phenyl-3-aminopropyltrimethoxysilane) per 100 parts of spherical silica (“SC1500SQ” manufactured by Admatex, average particle size 0.63 μm, specific surface area 11.2 m ^{2 / g).} KBM573) manufactured by Shin-Etsu Chemical Industry Co., Ltd. Surface-treated with 1 part.

[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), 5 parts of naphthalene type epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., epoxy equivalent of about 332), bisphenol AF type epoxy resin ( Mitsubishi Chemical Co., Ltd. "YL7760", epoxy equivalent about 238) 15 parts, cyclohexane type epoxy resin (Mitsubishi Chemical Co., Ltd. "ZX1658GS", epoxy equivalent about 135) 4 parts, phenoxy resin (Mitsubishi Chemical Co., Ltd. "YL7500BH30", solid content Two parts of 30% by mass of cyclohexanone: methyl ethyl ketone (MEK) 1: 1 solution, Mw = 44000) 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 3 parts of a triazine skeleton-containing novolac-based curing agent ("LA-7054" manufactured by DIC, MEK solution having a hydroxyl group equivalent of about 125 and a solid content of 60%), and a naphthol-based curing agent (DIC). Manufactured by "SN-495V", hydroxyl group equivalent of about 231) 6 parts, inorganic filler 1 80 parts, amine-based curing accelerator (4-dimethylaminopyridine (DMAP)) 0.05 parts are mixed, and a high-speed rotation mixer is used. After uniformly dispersing, 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), 5 parts of naphthalene type epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., epoxy equivalent of about 332), bisphenol AF type epoxy resin ( Mitsubishi Chemical Co., Ltd. "YL7760", epoxy equivalent about 238) 15 parts, cyclohexane type epoxy resin (Mitsubishi Chemical Co., Ltd. "ZX1658GS", epoxy equivalent about 135) 4 parts, phenoxy resin (Mitsubishi Chemical Co., Ltd. "YX7553BH30", solid content Two parts of 30% by mass of cyclohexanone: a 1: 1 solution of methyl ethyl ketone (MEK)) 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 triazine skeleton-containing cresol novolac-based curing agent (“LA-3018-50P” manufactured by DIC, hydroxyl group equivalent of about 151, 2-methoxypropanol solution having a solid content of 50%), activity. 7 parts of ester-based curing agent ("EXB-8000L-65M" manufactured by DIC, MEK solution having active group equivalent of about 220, 65% by mass of non-volatile component), 90 parts of inorganic filler 1, amine-based curing accelerator (4- 0.05 parts of dimethylaminopyridine (DMAP)) was mixed, uniformly dispersed with a high-speed rotary mixer, and then filtered through a cartridge filter (“SHP020” manufactured by ROKITECHNO) to prepare a resin composition 2.

<Preparation of resin composition 3>
6 parts of bixilenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent of about 185), 5 parts of naphthalene type epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., epoxy equivalent of about 332), bisphenol AF type epoxy resin ( Mitsubishi Chemical Co., Ltd. "YL7760", epoxy equivalent about 238) 15 parts, naphthylene ether type epoxy resin (DIC Co., Ltd. "EXA-7311-G4", epoxy equivalent about 213) 2 parts, phenoxy resin (Mitsubishi Chemical Co., Ltd. "" Two parts of "YX7553BH30" (1: 1 solution of cyclohexanone: methyl ethyl ketone (MEK) having a solid content of 30% by mass) 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 triazine skeleton-containing cresol novolac-based curing agent (“LA-3018-50P” manufactured by DIC, hydroxyl group equivalent of about 151, 2-methoxypropanol solution having a solid content of 50%), activity. 7 parts of ester-based 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 2, amine-based curing accelerator (4- 0.05 parts of dimethylaminopyridine (DMAP)) was mixed, uniformly dispersed with a high-speed rotary mixer, and then filtered through a cartridge filter (“SHP020” manufactured by ROKICHNO) 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), 5 parts of naphthalene type epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., epoxy equivalent of about 332), bisphenol AF type epoxy resin ( Mitsubishi Chemical Co., Ltd. "YL7760", epoxy equivalent about 238) 15 parts, naphthylene ether type epoxy resin (DIC Co., Ltd. "EXA-7311-G4", epoxy equivalent about 213) 2 parts, phenoxy resin (Mitsubishi Chemical Co., Ltd. "" YL7500BH30 ”, a 1: 1 solution of cyclohexanone: methyl ethyl ketone (MEK) having a solid content of 30% by mass, Mw = 44000) 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, 4 parts of a triazine skeleton-containing cresol novolac-based curing agent (“LA-3018-50P” manufactured by DIC, hydroxyl group equivalent of about 151, 2-methoxypropanol solution having a solid content of 50%), activity. 7 parts of ester-based 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 2, amine-based curing accelerator (4- 0.05 parts of dimethylaminopyridine (DMAP)) was mixed, uniformly dispersed with a high-speed rotary mixer, and then filtered through a cartridge filter (“SHP020” manufactured by ROKITECHNO) to prepare a resin composition 4.

<Preparation of resin composition 5>
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), cyclohexane type epoxy resin (Mitsubishi) 4 parts of "ZX1658GS" manufactured by Kagaku Co., Ltd., epoxy equivalent of about 135), 2 parts of phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Co., Ltd., 1: 1 solution of cyclohexanone: methyl ethyl ketone (MEK) with a solid content of 30% by mass), solvent naphtha It was dissolved by heating in a mixed solvent of 20 parts and 10 parts of cyclohexanone with stirring. After cooling to room temperature, there are 3 parts of a triazine skeleton-containing novolac-based curing agent ("LA-7054" manufactured by DIC, MEK solution having a hydroxyl group equivalent of about 125 and a solid content of 60%), and a naphthol-based curing agent (DIC). Manufactured by "SN-495V", hydroxyl group equivalent of about 231) 6 parts, inorganic filler 3 80 parts, amine-based curing accelerator (4-dimethylaminopyridine (DMAP)) 0.05 parts mixed, with a high-speed rotation mixer After uniformly dispersing, the resin composition 5 was prepared by filtering with a cartridge filter (“SHP020” manufactured by ROKICHNO).

<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 & Sumitomo Metal 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 triazine skeleton-containing cresol novolac-based curing agent (“LA-3018-50P” manufactured by DIC, hydroxyl group equivalent of about 151, 2-methoxypropanol solution having a solid content of 50%), activity. 7 parts of ester-based curing agent ("EXB-8000L-65M" manufactured by DIC, active group equivalent of about 220, MEK solution of 65% by mass of non-volatile component), 80 parts of inorganic filler 3, imidazole-based curing accelerator (1B2PZ, After 0.05 parts of 1-benzyl-2-phenylimidazole) were mixed and uniformly dispersed with a high-speed rotary mixer, the resin composition 6 was prepared by filtering with a cartridge filter (“SHP020” manufactured by ROKITECHNO).

The components used in the preparation of the resin compositions 1 to 6 and their blending amounts (parts by mass) 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 & Sumitomo Metal Corporation, epoxy equivalent about 332
EXA-7311-G4: Naftylene ether type epoxy resin, manufactured by DIC Corporation, epoxy equivalent about 213
YL7760: Bisphenol AF type epoxy resin, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent about 238
ZX1658GS: Cyclohexane type epoxy resin, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent about 135
LA-3018-50P: Triazine skeleton-containing cresol novolac-based curing agent, manufactured by DIC, 2-methoxypropanol solution having a hydroxyl group equivalent of about 151 and a solid content of 50% LA-7054: Triazine skeleton-containing novolac-based curing agent, manufactured by DIC, MEK solution SN-495V with a hydroxyl group equivalent of about 125 and a solid content of 60%: naphthol-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: methyl ethyl ketone ( MEK) 1: 1 solution YL7500BH30: Phenoxy resin, manufactured by Mitsubishi Chemical Corporation, cyclohexanone with a solid content of 30% by mass: 1: 1 solution of methyl ethyl ketone (MEK), Mw = 44000
DMAP: Amine-based curing accelerator, 4-dimethylaminopyridine

[Preparation of resin sheet A]
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 is uniformly applied on a release PET with a die coater so that the thickness of the resin composition layer after drying is 7.5 μm, and dried at 70 ° C. to 95 ° C. for 2 minutes. A resin composition layer was obtained on the release PET. 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 surface of the resin composition layer that is not bonded to the support. Laminated so as to. As a result, a resin sheet A composed of a release PET (support), a resin composition layer, and a protective film was obtained.

[Preparation of resin sheet B]
In the preparation of the resin sheet A, the resin composition layer was uniformly applied with a die coater so that the thickness of the resin composition layer after drying was 13 μm. A resin sheet B was obtained by producing the same as the resin sheet A except for the above items.

<Manufacturing of roughened substrate A and evaluation substrate A>
(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 film on the copper surface with "FlatBOND-FT" manufactured by MEC.

(2) Lamination of Resin Sheet A The protective film is peeled off from each resin sheet A 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) is used. Then, the resin composition layer was laminated on both sides of the inner layer circuit board so as to be 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 heat-cured 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 provide an insulating layer. Was formed, and the release PET was peeled off.

(4) Step of roughening treatment The inner layer circuit board on which the insulating layer was formed was subjected to desmear treatment as roughening treatment. As the desmear treatment, the following wet desmear treatment was carried out.

Wet desmear treatment:
In a swelling 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. This was designated as "roughened substrate A".

(5) Step of forming a conductor layer (5-1) Electroless plating step In order to form a conductor layer on the surface of the roughened substrate A that has been roughened, a plating step including the following steps 1 to 6 (5) A conductor layer was formed by performing a copper plating process) using a chemical solution manufactured by Atotech Japan.

1. 1. Alkaline cleaning (cleaning of the surface of the insulating layer with via holes and charge adjustment)
The surface of the roughened substrate A was washed with Cleaning Cleaner Security 902 (trade name) at 60 ° C. for 5 minutes.
2. Soft etching (cleaning inside the via hole)
The surface of the roughened substrate A was treated with an aqueous solution of sodium sulfate-acidic peroxodisulfate at 30 ° C. for 1 minute.
3. 3. Predip (Adjustment of charge on the surface of the insulating layer for Pd application)
The surface of the roughened substrate A was prepared by Pre. Treatment was performed at room temperature for 1 minute using Dip Neoganth B (trade name).
4. Granting an activator (giving Pd to the surface of the insulating layer)
The surface of the roughened substrate A was treated with Activator Neoganth 834 (trade name) at 35 ° C. for 5 minutes.
5. Reduction (Reduction of Pd applied to the insulating layer)
The surface of the roughened substrate A was subjected to 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 mixed solution of Basic Solution Printed MSK-DK (trade name), Copper solution Printganth MSK (trade name), Stabilizer Printganth MSK-DK (trade name), and Reducer Cu (trade name). The surface of A was treated at 35 ° C. for 20 minutes to form an electroless copper plating layer. 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 A".

<Manufacturing of roughened substrate B and evaluation substrate B>
In <Preparation of roughened substrate A and evaluation substrate A>, the resin sheet A used for forming the insulating layer was changed to the resin sheet B. Except for the above items, the roughened substrate B and the evaluation substrate B were produced in the same manner as in the above <Preparation of the roughened substrate A and the evaluation substrate A>.

[Evaluation test]
<Measurement of spacing between conductor layers (thickness of insulating layer between conductor layers)>
A cross section of the evaluation substrate A was observed using a FIB-SEM composite device (“SMI3050SE” manufactured by SII Nanotechnology Inc.). 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 is shown in the table below.
Further, the evaluation substrate A was changed to the evaluation substrate B, the same measurement was performed, and the results are shown in the table below.

<Measurement of Arithmetic Mean Roughness (Ra) and Ten-Point Average Roughness (Rz)>
Ra (Ra ( 5) The value and the Rz (5) value were obtained. The average value of each of the 6 points was calculated, and the result of rounding off the last digit is shown in the table below. Further, the roughened substrate A was changed to the roughened substrate B, and the same measurement was performed to obtain the Ra (10) value and the Rz (10) value. The average value of 6 points was calculated for each, and the results are shown in the table below.

Ra (5) / Ra (10) is calculated from the obtained Ra (5) value and Ra (10) value, and when 1 ≦ Ra (5) / Ra (10) ≦ 1.2 is satisfied, “ "○", if not satisfied, "×". Rz (5) / Rz (10) is calculated from the Rz (5) value and the Rz (10) value, and when 1 ≦ Rz (5) / Rz (10) ≦ 1.4 is satisfied, “◯” is satisfied. If not, it was marked as "x".

<Measurement of plating adhesion (plating peel strength)>
Make a notch in the conductor layer of the evaluation substrate A 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 testing machine AC-50C-SL). Using an Instron universal tester, the load (kgf / cm) when 35 mm was peeled off in the vertical direction at a speed of 50 mm / min was measured and used as the peel strength.
Further, the evaluation substrate A was changed to the evaluation substrate B, the same measurement was performed, and the results are shown in the table below.

<Evaluation of insulation reliability of insulation layer>
The highly accelerated life test device (ETAC "PM422") uses the circular conductor side with a diameter of 10 mm of the evaluation substrate A as a + electrode and the lattice conductor (copper) side of the inner layer circuit board connected to the land with a diameter of 1 mm as a-electrode. ”), And 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 (“ECM-100” manufactured by J-RAS). ). This measurement is performed 6 times, and if the resistance value of all 6 test pieces is 1.00 × 10 ⁷ Ω or more, “○”, and if even one of them ^{is less than 1.00 × 10 7} Ω, “×”. The evaluation results and insulation resistance values are 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.
Further, the evaluation substrate A was changed to the evaluation substrate B, the same measurement was performed, and the results are shown in the table below.

It can be seen that Examples 1 to 4 satisfying the above formulas (1) and (2) are excellent in insulation reliability, plating peel strength, etc. of the insulating layer even if the insulating layer is thin. On the other hand, in Comparative Examples 1 and 2 that do not satisfy the formula (1) or the formula (2), it can be seen that the plating peel strength is inferior to that of Examples 1 to 4 when the thickness of the insulating layer is about 10 μm. Further, in Comparative Examples 1 and 2, when the thickness of the insulating layer is about 5 μm, it can be seen that the insulation reliability and plating peel strength of the insulating layer are inferior to those of Examples 1 to 4.

It has been confirmed that in Examples 1 to 4, even when the components (D) to (E) are not contained, the same result as in the above-mentioned Examples is obtained, although the degree is different.

1 First conductor layer 11 Main surface of the first conductor layer 2 Second conductor layer 21 Main surface of the second conductor layer 3 Insulation layer t1 Spacing between the first conductor layer and the second conductor layer (first And the thickness of the insulating layer between the second conductor layers)
t2 Thickness of the entire insulating layer

Claims (6)

A support and a resin composition layer formed of the resin composition provided on the support are included.
The resin composition is a composition containing a curable resin, a curing agent, an inorganic filler having an average particle size of 0.05 μm to 0.35 μm, a thermoplastic resin, and a curing accelerator.
The curable resin contains a fluorine compound and
The thickness of the resin composition layer is 15 μm or less,
The surface of the first layer having a thickness of 5.0 ± 0.8 μm, which is a cured product obtained by thermosetting the resin composition at 100 ° C. for 30 minutes and further at 180 ° C. for 30 minutes, is manufactured by Atotech Japan. Immerse in Swelling Dip Security Gant P at 60 ° C for 5 minutes, in Atotech Japan's Concentrate Compact CP at 80 ° C for 10 minutes, and in Atotech Japan's Reduction Solution Security P at 40 ° C for 5 minutes. After that, the arithmetic mean roughness Ra (5) and the ten-point average roughness Rz (5) of the surface of the first layer, and
The surface of the second layer having a thickness of 10.0 ± 0.8 μm, which is a cured product obtained by thermosetting the resin composition at 100 ° C. for 30 minutes and further at 180 ° C. for 30 minutes, is manufactured by Atotech Japan. Immerse in Swelling Dip Security Gant P at 60 ° C for 5 minutes, in Atotech Japan's Concentrate Compact CP at 80 ° C for 10 minutes, and in Atotech Japan's Reduction Solution Security P at 40 ° C for 5 minutes. After that, the arithmetic mean roughness Ra (10) and the ten-point average roughness Rz (10) of the surface of the second layer are
1 ≤ Ra (5) / Ra (10) ≤ 1.2 (1)
1 ≦ Rz (5) / Rz (10) ≦ 1.4 (2)
Meet the relationship,
The first conductor layer, the second conductor layer, and the insulating layer formed between the first conductor layer and the second conductor layer are included, and the first conductor layer and the second conductor layer are included. A resin sheet for forming the insulating layer of a printed wiring board having a distance from and less than 6 μm. The resin sheet according to claim 1 , wherein the content of the inorganic filler is 50% by mass or more when the non-volatile component in the resin composition is 100% by mass. The resin sheet according to claim 1 or 2 , wherein the fluorine compound is a fluorine-containing epoxy resin. The resin sheet according to any one of claims 1 to 3 , wherein the thickness of the resin composition layer is 10 μm or less. Includes a first conductor layer, a second conductor layer, and an insulating layer formed between the first conductor layer and the second conductor layer.
A printed wiring board in which the distance between the first conductor layer and the second conductor layer is 6 μm or less.
A printed wiring board, wherein the insulating layer is a cured product of the resin composition layer of the resin sheet according to any one of claims 1 to 4. A semiconductor device including the printed wiring board according to claim 5.

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