TW201900764A - Resin composition layer - Google Patents

Abstract

Provided is a resin composition layer which can suppress a haloing phenomenon even with the small thickness, and can obtain an insulating layer capable of forming a via-hole in a good shape. The resin composition layer with the thickness smaller than or equal to 15 [mu]m has a resin composition. The resin composition includes: (A) an epoxy resin; (B) an aromatic hydrocarbon resin containing an aromatic ring as a monocyclic ring or a condensed ring having two or more hydroxyl groups; and (C) an inorganic filler having at least one of an average particle diameter smaller than or equal to 100 nm and a specific surface area greater than or equal to 15 m2/g.

Description

Resin composition layer

The present invention relates to a resin composition layer. Further, the present invention relates to a resin sheet including the resin composition layer; and a printed wiring board and a semiconductor device including the insulating layer formed of the cured product of the resin composition layer.

In recent years, in order to achieve miniaturization of electronic equipment, development of printed wiring boards has become more thin. Along with this, the wiring circuit of the inner substrate is developed to be fine. For example, Patent Document 1 discloses a resin sheet (attached film) which can correspond to a fine wiring including a support and a resin composition layer. [Prior Technical Literature] [Patent Literature]

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

[Problems to be solved by the invention]

In order to achieve further miniaturization and thinning of an electronic device, the inventors of the present invention have discussed the thinning of the resin composition layer of the resin sheet. As a result of the investigation, the inventors have found that when a thin resin composition layer is applied to an insulating layer, a halo phenomenon occurs after the formation of the through hole. Here, the halo phenomenon refers to a phenomenon in which the resin of the surrounding insulating layer of the through hole is discolored. Such a halo phenomenon is usually caused by deterioration of the resin around the through hole. Further, it is found that when the insulating layer having the halo phenomenon is subjected to the roughening treatment, the resin of the portion of the insulating layer in which the halo phenomenon has occurred (hereinafter sometimes referred to as "the halo portion") is roughened. It will be eroded and interlayer peeling will occur between the insulating layer and the inner substrate.

Further, the inventors have found that when a thin resin composition layer is applied to an insulating layer, it is difficult to control the shape of the through hole, and it is difficult to obtain a through hole having a good shape. Here, the shape of the through hole is "good" means that the taper ratio of the through hole is close to 1. Moreover, the taper ratio of the through holes refers to the ratio of the bottom diameter of the through holes to the top diameter.

All of the above problems have been caused by the thickness reduction of the resin composition layer, which is a novel problem that has not been known in the past. From the viewpoint of improving the conduction reliability between the layers of the printed wiring board, it is desirable to solve these problems.

The present invention has been made in view of the above-described problems, and an object of the invention is to provide a resin composition layer which can provide an insulating layer which can suppress a halo phenomenon and can form a through hole having a good shape even if the thickness is thin; A resin sheet of a resin composition layer; a printed wiring board including a thin insulating layer capable of suppressing a halo phenomenon and capable of forming a through hole having a good shape; and a semiconductor device including the above printed wiring board. [Means to solve the problem]

In order to solve the above problems, the inventors of the present invention have found that aromatic hydrocarbons containing (A) an epoxy resin and (B) an aromatic ring containing a single ring or a condensed ring having two or more hydroxyl groups are combined. The resin and (C) a resin composition of an inorganic filler having at least one of an average particle diameter of 100 nm or less and a specific surface area of 15 m ² /g or more can solve the above problems, and thus the present invention has been completed. That is, the present invention encompasses the following.

[1] A resin composition layer comprising a resin composition layer having a thickness of 15 μm or less of a resin composition, wherein the resin composition comprises (A) an epoxy resin and (B) a single ring having two or more hydroxyl groups. Or an aromatic hydrocarbon resin of an aromatic ring of a condensed ring, and (C) an inorganic filler having an average particle diameter of 100 nm or less. [2] A resin composition layer comprising a resin composition layer having a thickness of 15 μm or less of a resin composition, wherein the resin composition comprises (A) an epoxy resin and (B) a single ring having two or more hydroxyl groups. Or an aromatic hydrocarbon resin of an aromatic ring of a condensed ring, and (C) an inorganic filler having a specific surface area of 15 m ² /g or more. [3] The resin composition layer according to [1] or [2], wherein the component (B) is represented by the following formula (1) or formula (2): (In the formula (1), R ⁰ each independently represents a divalent hydrocarbon group, and n1 represents an integer of 0 to 6), (In the formula (2), R ¹ to R ⁴ each independently represent a hydrogen atom or a monovalent hydrocarbon group). [4] The resin composition layer according to any one of [1] to [3] wherein the component (B) is represented by the following formula (3) or (4): (in equation (3), n2 represents an integer from 0 to 6), (In the formula (4), R ¹ to R ⁴ each independently represent a hydrogen atom or a monovalent hydrocarbon group). [5] The resin composition layer according to any one of [1] to [4], wherein the amount of the component (B) is 5% by mass to 50% by mass based on 100% by mass of the resin component in the resin composition. quality%. [6] The resin composition layer according to any one of [1] to [5], wherein the amount of the component (C) is 50% by mass based on 100% by mass of the nonvolatile component in the resin composition. the above. [7] The resin composition layer according to any one of [1] to [6], which is used for forming an insulating layer for forming a conductor layer. [8] The resin composition layer according to any one of [1] to [7] which is used for forming an interlayer insulating layer of a printed wiring board. [9] The resin composition layer according to any one of [1] to [8] which is formed by an insulating layer having a through hole having a top diameter of 35 μm or less. [10] A resin sheet comprising a support and a resin composition layer according to any one of [1] to [9] provided on the support. [11] A printed wiring board comprising an insulating layer formed of a cured product of the resin composition layer according to any one of [1] to [9]. [12] A printed wiring board comprising: a first conductor layer, a second conductor layer, and a printed wiring board formed of an insulating layer between the first conductor layer and the second conductor layer, wherein the insulating layer has a thickness of 15 μm or less The insulating layer has a through hole having a top diameter of 35 μm or less, and the through hole has a taper ratio of 80% or more, and the edge of the bottom of the through hole has a halo distance of 5 μm or less, and is opposite to the bottom radius of the through hole. The halo ratio is 35% or less. [13] The printed wiring board according to [12], wherein a halo ratio with respect to a bottom radius of the through hole is 5% or more. [14] A semiconductor device comprising the printed wiring board according to any one of [11] to [13]. [Effect of the invention]

According to the present invention, it is possible to provide a resin composition layer which can provide an insulating layer which can suppress a halo phenomenon and which can form a through hole of a good shape even if the thickness is thin, and a resin sheet including the resin composition layer described above; A printed wiring board capable of suppressing a halo phenomenon and forming a thin insulating layer of a good shape through hole; and a semiconductor device including the above printed wiring board.

Hereinafter, embodiments and examples will be described, and the present invention will be described in detail. However, the present invention is not limited to the embodiments and the examples described below, and may be arbitrarily changed without departing from the scope of the invention.

In the following description, the "resin component" of the resin composition means a component in which the inorganic filler is excluded from among the nonvolatile components contained in the resin composition.

[1. Outline of Resin Composition Layer] The resin composition layer of the present invention is a layer of a thin resin composition having a thickness of a specific value or less. Further, the resin composition of the resin composition layer of the present invention comprises: (A) an epoxy resin; (B) an aromatic hydrocarbon resin containing an aromatic ring having a single ring or a condensed ring of two or more hydroxyl groups, And (C) an inorganic filler having at least one of an average particle diameter of 100 nm or less and a specific surface area of 15 m ² /g or more. Therefore, the resin composition contained in the resin composition layer of the present invention may include any of the first resin composition and the second resin composition described below.

The first resin composition includes (A) an epoxy resin, (B) an aromatic hydrocarbon resin containing an aromatic ring having a single ring or a condensed ring of two or more hydroxyl groups, and (C) an average particle diameter of 100 nm or less. Inorganic filler.

The second resin composition contains (A) an epoxy resin, (B) an aromatic hydrocarbon resin containing an aromatic ring as a single ring or a condensed ring having two or more hydroxyl groups, and (C) a specific surface area of 15 m ² /g. The above inorganic filler.

By using such a resin composition layer, a thin insulating layer can be obtained. Further, it is possible to obtain a desired effect of the present invention which can form a through hole having a good shape while suppressing the halo phenomenon in the obtained insulating layer.

[2. (A) component: epoxy resin] Examples of the epoxy resin as the component (A) include a bixylenol epoxy resin, a bisphenol A epoxy resin, and a bisphenol F epoxy resin. , bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolac type epoxy resin, phenol novolak type epoxy resin , tert-butyl-catechol epoxy resin, naphthalene epoxy resin, naphthol epoxy resin, fluorene epoxy resin, epoxy propyl amine epoxy resin, epoxy propyl ester ring Oxygen resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin , epoxy resin with spiral ring, cyclohexane epoxy resin, cyclohexane dimethanol epoxy resin, naphthyl ether epoxy resin, trimethylol epoxy resin, tetraphenylethane Type epoxy resin, etc. The epoxy resin may be used singly or in combination of two or more.

The resin composition is preferably an epoxy resin having two or more epoxy groups in one molecule as the (A) epoxy resin. From the viewpoint of remarkably obtaining the desired effect of the present invention, an epoxy resin having two or more epoxy groups in one molecule with respect to 100% by mass of the non-volatile component of the epoxy resin (A) The ratio is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

The epoxy resin is a liquid epoxy resin (hereinafter sometimes referred to as "liquid epoxy resin") at a temperature of 20 ° C, and a solid epoxy resin at a temperature of 20 ° C (sometimes called "Solid epoxy resin"). The resin composition may contain only a liquid epoxy resin as the (A) epoxy resin, and may contain only a solid epoxy resin, but it is preferable to contain a liquid epoxy resin and a solid epoxy resin in combination. By using a liquid epoxy resin and a solid epoxy resin as the (A) epoxy resin in combination, the flexibility of the resin composition layer can be improved, or the breaking strength of the cured product of the resin composition layer can be improved.

The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule, and more preferably an aromatic liquid having two or more epoxy groups in one molecule. Epoxy resin. Here, the "aromatic" epoxy resin means an epoxy resin having an aromatic ring in its molecule.

As the liquid epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol AF type epoxy resin, a naphthalene type epoxy resin, a epoxy propyl ester type epoxy resin, or the like is preferable. Epoxypropylamine type epoxy resin, phenol novolak type epoxy resin, alicyclic epoxy resin having ester skeleton, cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, propylene oxide The amide type epoxy resin and the epoxy resin having a butadiene structure are more preferably a bisphenol A type epoxy resin, a bisphenol F type epoxy resin or a cyclohexane type epoxy resin.

Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", and "HP4032SS" (naphthalene epoxy resin) manufactured by DIC Corporation; "828US" and "jER828EL" manufactured by Mitsubishi Chemical Corporation. 825", "Epikote 828EL" (bisphenol A type epoxy resin); "jER807" and "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol phenolic aldehyde) manufactured by Mitsubishi Chemical Corporation Varnish type epoxy resin); "630" and "630LSD" (epoxypropylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ZX1059" (bisphenol A type epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. "EX-721" (epoxypropyl ester type epoxy resin) manufactured by Nagase ChemteX Co., Ltd.; "CELLOXIDE 2021P" manufactured by DAICEL Co., Ltd. (aliphatic ring with ester skeleton) "Epoxy resin"; "PB-3600" manufactured by DAICEL Co., Ltd. (epoxy resin with butadiene structure); "ZX1658" and "ZX1658GS" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. (liquid 1,4-ring Oxypropylcyclohexane type epoxy resin). These may be used alone or in combination of two or more.

The solid epoxy resin is preferably a solid epoxy resin having three or more epoxy groups in one molecule, and more preferably an aromatic solid having three or more epoxy groups in one molecule. Epoxy resin.

As the solid epoxy resin, a bixylenol type epoxy resin, a naphthalene type epoxy resin, a naphthalene type tetrafunctional epoxy resin, a cresol novolak type epoxy resin, a dicyclopentadiene type epoxy resin is preferable. Resin, trisphenol epoxy resin, naphthol epoxy resin, biphenyl epoxy resin, naphthyl ether epoxy resin, fluorene epoxy resin, bisphenol A epoxy resin, bisphenol AF type The epoxy resin and the tetraphenylethane type epoxy resin are more preferably a dimethicone type epoxy resin, a naphthalene type epoxy resin, a bisphenol AF type epoxy resin, and a stretch naphthyl ether type epoxy resin.

Specific examples of the solid epoxy resin include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC Corporation; "HP-4700" and "HP-4710" manufactured by DIC Corporation (naphthalene type 4-functional epoxy) "N-690" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "HP-made by DIC Corporation" 7200" (dicyclopentadiene type epoxy resin); "HP-7200HH", "HP-7200H", "EXA-7311", "EXA-7311-G3", "EXA-7311-G4" manufactured by DIC Corporation "EXA-7311-G4S", "HP6000" (streptylene ether type epoxy resin); "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; manufactured by Nippon Kayaku Co., Ltd. "NC7000L" (naphthol novolak type epoxy resin); "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; Nippon Steel & Sumitomo Chemical Co., Ltd. "ESN475V" (naphthalene type epoxy resin); "ESN485" (naphthol novolak type epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.; "YX4000H" and "YX4000" manufactured by Mitsubishi Chemical Corporation YL6121" (biphenyl type epoxy resin); "YX4000HK" (dimethicone type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (蒽 type epoxy resin) manufactured by Mitsubishi Chemical Corporation; Osaka Gas Chemicals "PG-100" and "CG-500"; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL7800" (茀 type epoxy resin) manufactured by Mitsubishi Chemical Corporation; Mitsubishi Chemical Corporation "jER1010" (solid bisphenol A type epoxy resin) manufactured by the company; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation. These may be used alone or in combination of two or more.

In the case where a liquid epoxy resin and a solid epoxy resin are used in combination as the (A) epoxy resin, the ratio (liquid epoxy resin: solid epoxy resin) is preferably a mass ratio. It is 1:1~1:20, more preferably 1:2~1:15, especially good 1:5~1:13. By the ratio of the amount of the liquid epoxy resin to the solid epoxy resin being such a range, the desired effect of the present invention can be remarkably obtained. Further, when it is usually used in the form of a resin sheet, moderate adhesion can be obtained. Moreover, when it is used in the form of a resin sheet, sufficient flexibility can be obtained, and workability can be improved. Further, a cured product having a sufficient breaking strength can be usually obtained.

(A) The epoxy equivalent of the epoxy resin is preferably from 50 to 5,000, more preferably from 50 to 3,000, still more preferably from 80 to 2,000, still more preferably from 110 to 1,000. By setting it as this range, the bridge|crosslinking density of the hardened material of the resin composition layer becomes sufficient, and the insulation layer of the surface thickness is small. The epoxy equivalent is the mass of the resin containing 1 equivalent of the epoxy group. This epoxy equivalent can be measured in accordance with JIS K7236.

(A) The weight average molecular weight (Mw) of the epoxy resin is preferably from 100 to 5,000, more preferably from 250 to 3,000, still more preferably from 400 to 1,500, from the viewpoint of remarkably obtaining the desired effect of the present invention. . The weight average molecular weight of the resin can be measured by a gel permeation chromatography (GPC) method as a value in terms of polystyrene.

The amount of the (A) epoxy resin in the resin composition is preferably 100% by mass based on the resin component in the resin composition from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. It is 10% by mass or more, more preferably 20% by mass or more, and still more preferably 30% by mass or more. The upper limit of the content of the epoxy resin is preferably 90% by mass or less, more preferably 85% by mass or less, and particularly preferably 80% by mass or less from the viewpoint of obtaining the desired effect of the present invention.

[3. (B) component: an aromatic hydrocarbon resin containing an aromatic ring having a single ring or a condensed ring of two or more hydroxyl groups] The resin composition contains an aromatic hydrocarbon resin containing an aromatic ring having two or more hydroxyl groups As component (B). In general, the component (B) can be reacted with the (A) epoxy resin by the hydroxyl group of the aromatic ring, and therefore, the component (B) can function as a curing agent for hardening the resin composition. Further, by the action of the component (B), the halo phenomenon can be suppressed.

Here, the term "aromatic ring" includes either an aromatic ring which is a single ring such as a benzene ring, and an aromatic ring which is a condensed ring such as a naphthalene ring. The number of carbon atoms per one aromatic ring contained in the component (B) is preferably 6 or more, and preferably 14 or less, from the viewpoint of obtaining the desired effect of the present invention. Good for 10 or less.

Examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring and the like. In addition, the type of the aromatic ring to be contained in one molecule of the aromatic hydrocarbon resin may be one type or two or more types.

At least one of the aromatic rings contained in the aromatic hydrocarbon resin as the component (B) has two or more hydroxyl groups per one aromatic ring. The number of hydroxyl groups per one aromatic ring is preferably three or less, and particularly preferably two, from the viewpoint of obtaining the desired effect of the present invention remarkably.

The number of the aromatic rings having two or more hydroxyl groups per molecule of the component (B) is usually one or more, and from the viewpoint of obtaining the desired effect of the present invention remarkably, it is preferably two or more, and more preferably It is more than three. The upper limit is not particularly limited, but from the viewpoint of suppressing the steric hindrance from increasing the reactivity with the epoxy resin, it is preferably 6 or less, more preferably 5 or less.

Examples of the suitable component (B) include an aromatic hydrocarbon resin represented by the following formula (1) and an aromatic hydrocarbon resin represented by the following formula (2).

In the formula (1), R ⁰ each independently represents a divalent hydrocarbon group. The divalent hydrocarbon group may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group in which an aliphatic hydrocarbon group and an aromatic hydrocarbon group are combined. The number of carbon atoms of the divalent hydrocarbon group is usually 1 or more, and from the viewpoint of remarkably obtaining the desired effect of the present invention, it is preferably 3 or more, 6 or more, or 7 or more. The upper limit of the number of carbon atoms is preferably 20 or less, 15 or less, or 10 or less from the viewpoint of remarkably obtaining the desired effect of the present invention.

Specific examples of R ⁰ include the following hydrocarbon groups.

In the formula (1), n1 represents an integer of 0 or more and 6 or less. Among them, n1 is preferably 1 or more, more preferably 2 or more, and is preferably 4 or less, and more preferably 3 or less from the viewpoint of remarkably obtaining the desired effect of the present invention.

When the aromatic hydrocarbon resin represented by the formula (1) is used, the halo phenomenon can be particularly effectively suppressed.

In the formula (2), R ¹ to R ⁴ each independently represent a hydrogen atom or a monovalent hydrocarbon group. The monovalent hydrocarbon group may be an aliphatic hydrocarbon group, an aromatic hydrocarbon or a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group. Among them, from the viewpoint of remarkably obtaining the desired effect of the present invention, an aliphatic hydrocarbon group is preferred, a saturated aliphatic hydrocarbon group is more preferred, and a chain saturated aliphatic hydrocarbon group is particularly preferred. The number of carbon atoms of the monovalent hydrocarbon group is usually 1 or more, and from the viewpoint of obtaining the desired effect of the present invention remarkably, it is preferably 20 or less, more preferably 15 or less, 10 or less or 8 or less. Preferable examples of R ¹ to R ⁴ include a hydrogen atom; an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group or a hexyl group. When the aromatic hydrocarbon resin represented by the formula (2) is used, the peeling of the halo portion due to the erosion at the time of the roughening treatment can be particularly effectively suppressed.

In particular, the aromatic hydrocarbon resin represented by the following formula (3) and the aromatic hydrocarbon resin represented by the following formula (4) are exemplified as the aromatic hydrocarbon resin which is particularly preferable as the component (B). In the formula (3), n2 represents an integer defined by the same formula as n1 of the formula (1), and the preferred range is also the same. Further, in the formula (4), R ¹ to R ⁴ are synonymous with R ¹ to R ⁴ in the formula (2).

The commercially available product of the aromatic hydrocarbon resin represented by the formula (3) is, for example, a naphthol-based curing agent "SN395" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., which is represented by the following formula (5). In the formula (5), n3 represents 2 or 3. In addition, as a commercial item of the aromatic hydrocarbon resin represented by the formula (4), for example, the phenolic curing agent "GRA13H" manufactured by Kyoei Chemical Industry Co., Ltd. is mentioned.

The aromatic hydrocarbon resin as the component (B) may be used alone or in combination of two or more.

The hydroxyl equivalent of the component (B) is preferably 50 g/eq or more from the viewpoint of improving the crosslinking density of the insulating layer of the cured product of the resin composition layer and the effect of obtaining the desired effect of the present invention remarkably. More preferably, it is 60 g/eq or more, more preferably 70 g/eq or more, further preferably 200 g/eq or less, more preferably 150 g/eq or less, and particularly preferably 120 g/eq or less. The hydroxyl equivalent is the mass of the resin containing 1 equivalent of the hydroxyl group.

The amount of the component (B) in the resin composition is preferably 5% by mass or more, more preferably 7% by mass or more, and particularly preferably 9% by mass or more based on 100% by mass of the resin component in the resin composition. It is preferably 50% by mass or less, more preferably 40% by mass or less, 30% by mass or less or 20% by mass or less. By the amount of the component (B) being the aforementioned range, the halo phenomenon can be effectively suppressed.

The amount of the component (B) in 100% by mass of the (A) epoxy resin is preferably 5% by mass or more, more preferably 8% by mass or more, particularly preferably 10% by mass or more, and preferably 100% by mass. Hereinafter, it is more preferably 50% by mass or less, and particularly preferably 30% by mass or less. By the amount of the component (B) being the aforementioned range, the halo phenomenon can be effectively suppressed.

When the number of epoxy groups of the (A) epoxy resin is 1, the number of hydroxyl groups of the component (B) is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.3 or more, and preferably 2 Hereinafter, it is more preferably 1.5 or less, still more preferably 1 or less, and particularly preferably 0.5 or less. Here, "(A) the number of epoxy groups of the epoxy resin" means a value obtained by dividing the mass of the nonvolatile component of the component (A) present in the resin composition by the value of the epoxy equivalent. In addition, the "number of hydroxyl groups of the component (B)" means a value obtained by dividing the mass of the nonvolatile component of the component (B) present in the resin composition by the value of the hydroxyl equivalent. When the number of hydroxyl groups of the component (B) in the (A) epoxy group is set to 1, the halo phenomenon can be effectively suppressed.

[4. (C) component: an inorganic filler having an average particle diameter of 100 nm or less and a specific surface area of 15 m ² /g or more] The resin composition contains an inorganic filler as the component (C). According to the inorganic filler, since the thermal expansion coefficient of the cured product of the resin composition layer can be reduced, an insulating layer in which the warpage of the reflow is suppressed can be obtained. Further, the inorganic filler as the component (C) has at least one of an average particle diameter of 100 nm or less and a specific surface area of 15 m ² /g or more. By using the (C) component which is at least one of the average particle diameter and the specific surface area of the inorganic filler as the inorganic filler in combination with the component (B), an insulating layer which can form a through hole of a good shape can be realized. .

As the material of the inorganic filler, an inorganic compound is used. Examples of the material of the inorganic filler include cerium oxide, aluminum oxide, glass, cordierite, cerium oxide, barium sulfate, cerium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, and gibbsite. , aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, barium carbonate, barium titanate, calcium titanate, magnesium titanate, titanic acid Bismuth, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium phosphotungstate, and the like. Among these, cerium oxide is particularly suitable. Examples of the cerium oxide include amorphous cerium oxide, molten cerium oxide, crystalline cerium oxide, synthetic cerium oxide, and hollow cerium oxide. Further, as the cerium oxide, spherical cerium oxide is preferred. The inorganic filler may be used singly or in combination of two or more.

The average particle diameter of the component (C) is usually 100 nm or less, preferably 90 nm or less, and more preferably 80 nm from the viewpoint of reducing the thickness of the insulating layer and controlling the shape of the via hole to achieve a good shape. the following. The lower limit of the average particle diameter is not particularly limited, but is preferably 50 nm or more, 60 nm or more, or 70 nm or more. As a commercial item of the inorganic filler which has such an average particle diameter, the "UFP-30" and the "UFP-40" by the electrochemical industrial company are mentioned, for example.

The average particle size of the inorganic filler can be determined by a laser diffraction/scattering method according to the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis by a laser diffraction scattering type particle size distribution measuring apparatus, and the median diameter can be measured as an average particle diameter. As the measurement sample, those in which the inorganic filler is dispersed in methyl ethyl ketone by ultrasonic waves can be preferably used. As the laser diffraction scattering type particle size distribution measuring apparatus, "LA-500" manufactured by Horiba, Ltd., and "SALD-2200" manufactured by Shimadzu Corporation can be used.

The specific surface area of the component (C) is usually 15 m ² /g or more, preferably 20 m ² /g or more, and particularly preferably 30 m ² / from the viewpoint of easily controlling the shape of the through hole. g or more. Further, in the case of the component (C) having a large specific surface area, in general, since the particle diameter is small, the insulating layer can be made thin. The upper limit is not particularly limited, but is preferably 60 m ² /g or less, 50 m ² /g or less, or 40 m ² /g or less. The specific surface area of the inorganic filler can be measured by the BET method.

The inorganic filler as the component (C) is preferably treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Examples of the surface treatment agent include a fluorine-containing decane coupling agent, an amino decane coupling agent, an epoxy decane coupling agent, a mercapto decane coupling agent, a decane coupling agent, an alkoxy decane, and an organic decane compound. , a titanate coupling agent, and the like. Further, the surface treatment agent may be used singly or in combination of two or more kinds.

For example, "KBM403" (3-glycidoxypropyltrimethoxydecane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-Mercaptopropyl C) manufactured by Shin-Etsu Chemical Co., Ltd. "Ketium methoxy decane", "KBE903" (3-aminopropyltriethoxy decane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" manufactured by Shin-Etsu Chemical Co., Ltd. (N-phenyl-3-aminopropyltrimethyl) "oxyzane", "SZ-31" (hexamethyldiazane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM103" (phenyltrimethoxydecane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-" manufactured by Shin-Etsu Chemical Co., Ltd. 4803" (long-chain epoxy decane coupling agent), "KBM-7103" (3,3,3-trifluoropropyltrimethoxydecane) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

The degree of surface treatment by the surface treatment agent is preferably within a specific range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, 100 parts by mass of the inorganic filler, preferably 0.2 parts by mass to 5 parts by mass of the surface treatment agent, is preferably surface-treated with 0.2 parts by mass to 3 parts by mass, preferably 0.3. The mass parts are ~2 parts by mass for surface treatment.

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

The amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed by a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent was added to the inorganic filler which was surface-treated with a surface treatment agent, and ultrasonic cleaning was performed at 25 ° C for 5 minutes. After the supernatant liquid is removed and the solid component is dried, a carbon analyzer is used to determine the amount of carbon per unit surface area of the inorganic filler. As the carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. can be used.

The amount of the component (C) in the resin composition is preferably 30% by mass or more based on 100% by mass of the nonvolatile component in the resin composition, from the viewpoint of lowering the dielectric tangent of the insulating layer. More preferably, it is 35 mass% or more, and still more preferably 40 mass% or more. In addition, in the case where the layer of the resin composition containing a large amount of the inorganic filler is thin, it is difficult to make the shape of the through hole favorable, in particular, if the amount of the inorganic filler is relative to the resin composition. When the nonvolatile component is 100% by mass or more and is 50% by mass or more, it is particularly difficult to form a through hole system having a good shape. Therefore, from the viewpoint of effectively utilizing the advantages of the present invention which can form a through-hole having a shape which is particularly difficult in the past, the amount of the component (C) is 100% by mass relative to the non-volatile component in the resin composition. It is preferably 50% by mass or more, and particularly preferably 54% by mass or more. The upper limit of the amount of the component (C) is preferably 90% by mass or less, and more preferably 85% by mass or less from the viewpoint of increasing the mechanical strength of the insulating layer with respect to 100% by mass of the nonvolatile component in the resin composition. More preferably, it is 80 mass% or less, or 75 mass% or less.

[5. Component (D): Thermoplastic Resin] The resin composition may further contain (D) a thermoplastic resin as an optional component in addition to the above components.

Examples of the thermoplastic resin as the component (D) include a phenoxy resin, a polyvinyl acetal resin, a polyolefin resin, a polybutadiene resin, a polyimide resin, a polyamide amide resin, and a polyether. A quinone imine resin, a polyfluorene resin, a polyether oxime resin, a polyphenylene ether resin resin, a polycarbonate resin, a polyether ether ketone resin, a polyester resin, or the like. Among them, from the viewpoint of obtaining the desired effect of the present invention remarkably, and obtaining an insulating layer which is particularly excellent in adhesion to a conductor layer having a small surface roughness, a phenoxy resin is preferable. Further, the thermoplastic resin may be used singly or in combination of two or more.

The phenoxy resin may, for example, be selected from the group consisting of a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a novolak skeleton, a biphenyl skeleton, an anthracene skeleton, and a dicyclopentane. A phenoxy resin having at least one of a diene skeleton, a norbornene skeleton, a naphthalene skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any one of a phenolic hydroxyl group and an epoxy group.

Specific examples of the phenoxy resin include "1256" and "4250" manufactured by Mitsubishi Chemical Corporation (both phenoxy resins containing a bisphenol A skeleton); "YX8100" manufactured by Mitsubishi Chemical Corporation (including double "Phenyl resin of phenol S skeleton"; "YX6954" manufactured by Mitsubishi Chemical Corporation (phenoxy resin containing bisphenol acetophenone skeleton); "FX280" and "FX293" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.; Mitsubishi "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290" and "YL7482" manufactured by Chemical Company.

The polyvinyl acetal resin may, for example, be a polyethylene formaldehyde resin or a polyvinyl butyral resin, preferably a polyvinyl butyral resin. Specific examples of the polyvinyl acetal resin include "Denka Butyral 4000-2", "Denka Butyral 5000-A", "Denka Butyral 6000-C", and "Denka Butyral 6000-EP" manufactured by Denki Kogyo Co., Ltd. S-LEC BH series, BX series (such as BX-5Z), KS series (such as KS-1), BL series, BM series, etc. manufactured by Sekisui Chemical Industry Co., Ltd.

Specific examples of the polyimine resin include "RIKACOAT SN20" and "RIKACOAT PN20" manufactured by Nippon Chemical and Chemical Co., Ltd. Specific examples of the polyimine resin include a linear polyimine obtained by reacting a bifunctional hydroxyl-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride (JP-A-2006-37083) The polycondensation of poly-imines, which are described in the above-mentioned publications, and poly-imines, which are described in JP-A-2002-210667 and JP-A-2000-319386, etc. Yttrium.

Specific examples of the polyamidoximine resin include "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of the polyamidoximine resin include denatured polyamides such as "KS9100" and "KS9300" (polyamidoquinone containing a polyoxyalkylene skeleton) manufactured by Hitachi Chemical Co., Ltd. Imine.

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

Specific examples of the polyphenylene ether resin include oligo phenylene ether (OPE) manufactured by Mitsubishi Gas Chemical Co., Ltd., styrene resin "OPE-2 St 1200", and the like.

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

The weight average molecular weight (Mw) of the thermoplastic resin (D) is preferably 8,000 or more, more preferably 10,000 or more, particularly preferably 20,000 or more, and more preferably from the viewpoint of remarkably obtaining the desired effect of the present invention. 70,000 or less, more preferably 60,000 or less, and particularly preferably 50,000 or less.

In the case of using the (D) thermoplastic resin, the amount of the (D) thermoplastic resin in the resin composition is 100% by mass from the resin composition in terms of the desired effect of the present invention. % is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, and is preferably 15% by mass or less, more preferably 12% by mass or less, and still more preferably 10% by mass or less.

[6. (E) component: curing agent] The resin composition may further contain (E) a curing agent other than the component (B) as an optional component in addition to the above components.

As the hardener of the component (E), those having an action of hardening the component (A) can be used. Examples of the (E) curing agent include an active ester-based curing agent, a phenol-based curing agent, a naphthol-based curing agent, and benzo. A azine-based curing agent, a cyanate-based curing agent, and a carbodiimide-based curing agent. Further, the curing agent may be used singly or in combination of two or more. Among them, from the viewpoint of remarkably obtaining the desired effects of the present invention, an active ester-based curing agent is preferred.

As the active ester-based curing agent, a compound having one or more active ester groups in one molecule can be used. In particular, the active ester-based curing agent is preferably an ester having two or more reactive groups in one molecule, such as a phenol ester, a thiophenol ester, an N-hydroxylamine, or an ester of a heterocyclic hydroxy compound. Base compound. The active ester-based curing agent is preferably obtained by a condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of heat resistance improvement, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester system derived from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferred. hardener.

Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.

Examples of the phenol compound or the naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, and methyl group. Bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-di Hydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxydiphenyl ketone, trihydroxydiphenyl ketone, tetrahydroxydiphenyl ketone, cadaverin, benzenetriol, dicyclopentadiene type diphenol compound , phenol novolac and the like. Here, the "dicyclopentadiene type diphenol compound" means a diphenol compound obtained by condensing a molecule of dicyclopentadiene with a molecule of phenol 2.

Preferred examples of the active ester-based curing agent include an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, and an active ester compound containing an acetal of a phenol novolak. An active ester compound comprising a benzamidine phenolic novolac. Among them, an active ester compound containing a naphthalene structure or an active ester compound containing a dicyclopentadiene type diphenol structure is more preferable. The "dicyclopentadiene type diphenol structure" means a divalent structural unit composed of a phenyl-bicyclopentyl-phenylene group.

As a commercial product of the active ester-based curing agent, "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", which are active ester compounds containing a dicyclopentadiene-type diphenol structure, may be mentioned. "EXB9416-70BK" (manufactured by DIC Corporation), which is an active ester compound containing a naphthalene structure, as "HPC-8000H-65TM", "EXB-800L-65TM", "EXB-8150-65T" (manufactured by DIC Corporation); "DC808" (manufactured by Mitsubishi Chemical Corporation), which is an active ester compound of an acetal phenolic aldehyde varnish, and "YLH1026" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound of a benzoic acid phenolic phenol varnish; "DC808" (manufactured by Mitsubishi Chemical Corporation), an active ester-based hardener of acetaldehyde varnish, and "YLH1026" (manufactured by Mitsubishi Chemical Corporation), which is an active ester-based hardener of benzamidine phenolic varnish. YLH1030 (manufactured by Mitsubishi Chemical Corporation) and "YLH1048" (manufactured by Mitsubishi Chemical Corporation).

The phenolic curing agent and the naphthol-based curing agent are preferably those having a novolak structure from the viewpoint of heat resistance and water resistance. Moreover, 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 phenolic curing agent and the naphthol-based curing agent include "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Mingwa Chemical Co., Ltd., and "NHN" manufactured by Nippon Kayaku Co., Ltd. "CBN", "GPH"; "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V" and "SN375" made by Nippon Steel & Sumitomo Chemical Co., Ltd. DIC Corporation's "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500", etc.

Benzo Specific examples of the azine-based sizing agent include "HFB2006M" manufactured by Showa Polymer Co., Ltd., and "Pd" and "Fa" manufactured by Shikoku Chemical Industries Co., Ltd.

Examples of the cyanate-based curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylenecyanate), and 4,4'. -methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2- Bis(4-cyanate) phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1, 3-bis(4-cyanate phenyl-1-(methylethylidene)) benzene, bis(4-cyanate phenyl) sulfide, and bis(4-cyanate phenyl) ether a bifunctional cyanate resin; a polyfunctional cyanate resin derived from a phenol novolak and a cresol novolak; and a pre-polymerized triazine-based prepolymer such as a part of the cyanate resin. Specific examples of the cyanate-based curing agent include "PT30" and "PT60" (phenol novolac type polyfunctional cyanate resin) manufactured by Lonza Japan Co., Ltd., and "ULL-950S" (polyfunctional cyanate). Resin), "BA230", "BA230S75" (a part or all of bisphenol A dicyanate is triazineized to form a prepolymer of a terpolymer).

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

In the case of using the (E) hardener, the amount of the (E) hardener in the resin composition is 100% by mass relative to the resin component in the resin composition from the viewpoint of remarkably obtaining the desired effect of the present invention. The amount is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, and is preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably 12% by mass or more. Below mass%.

Further, in the case of using the (E) curing agent, the amount of the (E) curing agent in the resin composition is 100% by mass relative to the component (B) from the viewpoint of remarkably obtaining the desired effect of the present invention. In particular, it is preferably 40% by mass or more, more preferably 50% by mass or more, particularly preferably 60% by mass or more, and preferably 120% by mass or less, more preferably 100% by mass or less, and particularly preferably 90% by mass or less. .

Further, when the number of epoxy groups of the (A) epoxy resin is 1, the active group of the component (E) is preferably 0.1 or more, more preferably 0.2 or more, and still more preferably 2 or less, more preferably 1.5 or less, more preferably 1 or less, and particularly preferably 0.5 or less. Here, the "activity group of the component (E)" means a value obtained by dividing the mass of the non-volatile component of the component (E) present in the resin composition by the value of the active group equivalent. When the number of active groups of the component (E) in the (A) epoxy group is set to 1, the insulating layer is particularly excellent in mechanical strength.

[7. (F) Component: Hardening Accelerator] The resin composition may further contain (F) a curing accelerator as an optional component in addition to the above components.

Examples of the curing accelerator include a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, an oxime-based curing accelerator, and a metal-based curing accelerator. Among them, a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, and a metal-based curing accelerator are preferable, and an amine-based curing accelerator, an imidazole-based curing accelerator, and a metal-based curing accelerator are more preferable. The curing accelerator may be used singly or in combination of two or more.

Examples of the phosphorus-based hardening accelerator include triphenylphosphine, strontium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, and tetrabutylphosphonate. (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, etc., preferably triphenylphosphine, tetrabutylphosphonium Citrate.

Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, and 2,4,6- Ginseng (dimethylaminomethyl) phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc., preferably 4-dimethylaminopyridine, 1,8-di Azabicyclo(5,4,0)-undecene.

Examples of the imidazole-based hardening accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methyl. Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole , 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4 -methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecyl trimellitic acid imidazolium salt, 1-cyanoethyl-2-phenyl trimellitic acid Imidazole salt, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'- Undecylimidazo-(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 iso-cyanuric acid adduct , 2-phenylimidazolium isocyanurate adduct, 2-phenyl-4,5-dimethylolimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3 -Dihydroxy-1H-pyrrole[1,2-a]benzimidazole, 1-dodecyl-2- An imidazole compound such as methyl-3-benzylimidazolium chloride, 2-methylimidazoline or 2-phenylimidazoline, and an adduct of an imidazole compound and an epoxy resin, preferably 2-ethyl-4 -methylimidazole, 1-benzyl-2-phenylimidazole.

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

Examples of the oxime-based hardening accelerator include dicyandiamide, 1-methyl hydrazine, 1-ethyl hydrazine, 1-cyclohexyl fluorene, 1-phenyl fluorene, and 1-(o- 胍, dimethyl hydrazine, diphenyl hydrazine, trimethyl hydrazine, tetramethyl hydrazine, pentamethyl hydrazine, 1,5,7-triazabicyclo[4.4.0] fluorene-5-ene, 7-Methyl-1,5,7-triazabicyclo[4.4.0]non-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n- Octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenylbiguanide, 1-(o- The bismuth, etc., is preferably dicyandiamide or 1,5,7-triazabicyclo[4.4.0]non-5-ene.

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) acetate, cobalt (III), and copper (II). , an organic zinc complex such as acetonitrile zinc (II), an organic iron complex such as iron(III) acetonate, an organic nickel complex such as acetonitrile acetone (II), or manganese acetylacetonate (II) Organic manganese complexes, etc. Examples of the organic metal salt include zinc octoate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

In the case where the (F) hardening accelerator is used, the amount of the (F) hardening accelerator in the resin composition is 100% by mass of the resin component with respect to the resin composition from the viewpoint of remarkably obtaining the desired effect of the present invention. % is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, and is preferably 3% by mass or less, more preferably 2% by mass or less, and still more preferably 1.5% by mass or less.

[8. (G) component: optional additive] The resin composition may further contain any additive as an optional component in addition to the above components. Examples of such an additive include organic fillers; organometallic compounds such as organic copper compounds, organozinc compounds, and organic cobalt compounds; flame retardants, tackifiers, antifoaming agents, leveling agents, and adhesion imparting agents. Resin additives such as agents and colorants. These additives may be used alone or in combination of two or more.

[9. Thickness of Resin Composition Layer] The resin composition layer is a layer formed of the above-described resin composition and has a thickness of a specific value or less. The specific thickness of the resin composition layer is usually 15 μm or less, preferably 14 μm or less, and more preferably 12 μm or less. Conventionally, the thickness of the resin composition layer for forming an insulating layer of a printed wiring board is generally thick. On the other hand, the inventors of the present invention found that the resin composition layer of the general composition was thinned as described above, and found in the thin resin composition layer to cause occurrence of a halo phenomenon and shape control of the through hole. The previously unknown subject of difficulty. The resin composition layer of the present invention is thinner as described above from the viewpoint of solving such a novel problem and providing a thin film of a printed wiring board. The lower limit of the thickness of the resin composition layer is arbitrary, and may be, for example, 1 μm or more and 3 μm or more.

[10. Characteristics of Resin Composition Layer] By curing the resin composition layer of the present invention, a thin insulating layer formed of a cured product of the resin composition layer can be obtained. In this insulating layer, a through hole of a good shape can be formed. Further, when the through hole is formed in the insulating layer, the halo phenomenon can be suppressed. Hereinafter, the effects will be described with reference to the drawings.

Fig. 1 is a cross-sectional view schematically showing an insulating layer 100 and an inner layer substrate 200 obtained by curing a resin composition layer according to the first embodiment of the present invention. In the first drawing, a cross section in which the insulating layer 100 is cut is shown on a plane passing through the center 120C of the bottom portion 120 of the through hole 110 and parallel to the thickness direction of the insulating layer 100. As shown in Fig. 1, the insulating layer 100 according to the first embodiment of the present invention is a layer obtained by curing a resin composition layer formed on the inner layer substrate 200 including the conductor layer 210, and the resin composition layer is formed. It consists of a hardened material. Further, a through hole 110 is formed in the insulating layer 100. The through hole 110 is generally formed such that the diameter of the surface 100U of the insulating layer 100 on the side opposite to the conductor layer 210 is larger, and the closer to the diameter of the conductor layer 210, the smaller the tapered shape is formed. The insulating layer 100 has a columnar shape having a certain diameter in the thickness direction. The through hole 110 is usually formed by irradiating a surface 100U of the insulating layer 100 on the opposite side of the conductor layer 210 with a portion of the insulating layer 100 by irradiating the laser light.

The bottom of the via hole 110 on the side of the conductor layer 210 is appropriately referred to as a "hole bottom" and is denoted by reference numeral 120. Further, the diameter of the hole bottom 120 is referred to as a bottom diameter Lb. Moreover, the opening formed on the opposite side of the via hole 110 from the conductor layer 210 is appropriately referred to as a "hole top" and is denoted by reference numeral 130. Also, the diameter of the hole top 130 is referred to as the top diameter Lt. Usually, the planar shape of the hole bottom 120 and the hole top 130 viewed from the thickness direction of the insulating layer 100 is formed into a circular shape, but may be an elliptical shape. In the case where the planar shape of the hole bottom 120 and the hole top 130 is an elliptical shape, the bottom diameter Lb and the top diameter Lt respectively indicate the long diameter of the elliptical shape described above.

At this time, the closer the taper ratio Lb/Lt (%) obtained by dividing the bottom diameter Lb by the top diameter Lt is closer to 100%, the better the shape of the through hole 110 is. When the resin composition layer of the present invention is used, the shape of the through hole 110 can be easily controlled, and therefore, the through hole 110 having a taper ratio Lb/Lt close to 100% can be realized.

For example, the insulating layer 100 obtained by heating the resin composition layer at 100 ° C for 30 minutes, and then heating at 180 ° C for 30 minutes, has a mask diameter of 1 mm, a pulse width of 16 μs, and an energy of 0.2 mJ/shot. In the case of the number 2, the burst mode (10 kHz), the CO ₂ laser light is irradiated to form the via hole 110 having the top diameter Lt of 30 μm ± 2 μm. In this case, the through hole 110 may be tapered by Lb/Lt. It is preferably 60% to 100%, more preferably 70% to 100%, and particularly preferably 80% to 100%.

The taper ratio Lb/Lt of the through hole 110 can be calculated from the bottom diameter Lb of the through hole 110 and the top diameter Lt. Moreover, the bottom diameter Lb and the top diameter Lt of the through hole 110 can be made to be parallel to the thickness direction of the insulating layer 100 and pass through the center 120C of the hole bottom 120 by using FIB (Focused Ion Beam). After the shape of the cross section was cut out, the cross section was observed by an electron microscope and measured.

Fig. 2 is a plan view schematically showing a surface 100U of the insulating layer 100 obtained by curing the resin composition layer of the first embodiment of the present invention on the side opposite to the conductor layer 210 (not shown in Fig. 2). As shown in FIG. 2, when the insulating layer 100 in which the through holes 110 are formed is observed, the halo portion 140 in which the insulating layer 100 is discolored is observed around the through holes 110. The halo portion 140 is formed by a halo phenomenon when the through hole 110 is formed, and is generally formed continuously from the through hole 110. Further, in many cases, the halo portion 140 is a whitened portion.

By using the resin composition layer of the present invention, the aforementioned halo phenomenon can be suppressed. Therefore, the size of the halo portion 140 can be reduced, and it is desirable that the halo portion 140 can be eliminated. The size of the halo portion 140 can be evaluated by the halo distance Wt from the edge 150 of the aperture top 130 of the through hole 110.

The edge 150 of the hole top 130 corresponds to the edge of the inner peripheral side of the halo portion 140. The halo distance Wt from the edge 150 of the hole top 130 indicates the distance from the edge 150 of the hole top 130 to the edge portion 160 on the outer peripheral side of the halo portion 140. The smaller the halo distance Wt from the edge 150 of the hole top 130, the better the halo phenomenon can be effectively suppressed.

For example, the insulating layer 100 obtained by heating the resin composition layer at 100 ° C for 30 minutes, and then heating at 180 ° C for 30 minutes, has a mask diameter of 1 mm, a pulse width of 16 μs, and an energy of 0.2 mJ/shot. In the case of the number 2, the burst mode (10 kHz), the CO ₂ laser light is irradiated to form a through hole 110 having a top diameter Lt of 30 μm ± 2 μm. In this case, the edge 150 of the hole top 130 can be used as a halo The distance Wt is preferably 6 μm or less, more preferably 5 μm or less.

The halo distance Wt from the edge 150 of the hole top 130 can be determined by observation with an optical microscope.

Further, according to the investigation by the inventors of the present invention, it has been found that the larger the diameter of the through hole 110 is, the larger the size of the halo portion 140 tends to be. Thus, the degree of suppression of the halo phenomenon can be evaluated by the ratio of the size of the halo portion 140 to the diameter of the through hole 110. For example, it can be evaluated by the halo ratio Ht with respect to the top radius Lt/2 of the through hole 110. Here, the top radius Lt/2 of the through hole 110 refers to the radius of the hole top 130 of the through hole 110. Further, the halo ratio Ht with respect to the top radius Lt/2 of the through hole 110 is a ratio obtained by dividing the halo distance Wt from the edge 150 of the hole top 130 by the top radius Lt/2 of the through hole 110. The smaller the halo ratio Ht with respect to the top radius Lt/2 of the through hole 110, the more effectively the halo phenomenon can be suppressed.

For example, the insulating layer 100 obtained by heating the resin composition layer at 100 ° C for 30 minutes, and then heating at 180 ° C for 30 minutes, has a mask diameter of 1 mm, a pulse width of 16 μs, and an energy of 0.2 mJ/shot. In the case of the number 2, the burst mode (10 kHz), the CO ₂ laser light is irradiated to form the via hole 110 having the top diameter Lt of 30 μm ± 2 μm. In this case, the hole radius Lt/2 with respect to the via hole 110 can be obtained. The halo ratio is preferably 45% or less, more preferably 40% or less, still more preferably 35% or less.

The halo ratio Ht with respect to the top radius Lt/2 of the through hole 110 can be calculated from the top diameter Lt of the through hole 110 and the halo distance Wt from the edge 150 of the hole top 130 of the through hole 110.

Fig. 3 is a cross-sectional view showing the insulating layer 100 and the inner substrate 200 after the roughening treatment obtained by curing the resin composition layer of the first embodiment of the present invention. In the third drawing, a cross section in which the insulating layer 100 is cut is shown on a plane passing through the center 120C of the hole bottom 120 of the through hole 110 and parallel to the thickness direction of the insulating layer 100. As shown in FIG. 3, if the insulating layer 100 having the via holes 110 is subjected to the roughening treatment, the insulating layer 100 of the halo portion 140 is peeled off from the conductor layer 210, and is formed from the edge 170 of the hole bottom 120. A continuous gap portion 180. This gap portion 180 is usually formed by erosion of the halo portion 140 during the roughening process.

By using the resin composition layer of the present invention, the halo phenomenon can be suppressed as described above. Therefore, the size of the halo portion 140 can be reduced, and it is desirable that the halo portion 140 can be eliminated. Therefore, since the peeling from the insulating layer 100 of the conductor layer 210 can be suppressed, the size of the gap portion 180 can be reduced.

The edge 170 of the hole bottom 120 corresponds to the edge portion on the inner peripheral side of the gap portion 180. Therefore, the distance Wb from the edge 170 of the hole bottom 120 to the outer peripheral end portion of the gap portion 180 (that is, the end portion away from the center 120C side of the hole bottom 120) 190 corresponds to the in-plane of the gap portion 180. The size of the direction. Here, the in-plane direction means a direction perpendicular to the thickness direction of the insulating layer 100. Further, in the following description, the aforementioned distance Wb may be referred to as a halo distance Wb from the edge 170 of the hole bottom 120 of the through hole 110.

The degree of suppression of the formation of the gap portion 180 can be evaluated by the halo distance Wb from the edge 170 of the hole bottom 120. Specifically, the smaller the halo distance Wb from the edge 170 of the hole bottom 120, the more it can be evaluated that the formation of the gap portion 180 can be effectively suppressed.

Further, since the gap portion 180 is formed by peeling off the insulating layer 100 of the halo portion 140, the size thereof is related to the size of the halo phenomenon 140. Thus, the smaller the halo distance Wb from the edge 170 of the hole bottom 120, the more it can be evaluated that the halo phenomenon can be effectively suppressed.

For example, the insulating layer 100 obtained by heating the resin composition layer at 100 ° C for 30 minutes, and then heating at 180 ° C for 30 minutes, has a mask diameter of 1 mm, a pulse width of 16 μs, and an energy of 0.2 mJ/shot. In the case of the number 2 and the burst mode (10 kHz), the CO ₂ laser light was irradiated to form the via hole 110 having the top diameter Lt of 30 μm ± 2 μm. Thereafter, the mixture was immersed in a swelling solution at 60 ° C for 10 minutes, and then immersed in an oxidizing agent solution at 80 ° C for 20 minutes, followed by immersion in a neutralizing solution at 40 ° C for 5 minutes, followed by drying at 80 ° C for 15 minutes. In the case where such a roughening treatment is performed, the halo distance Wb from the edge 170 of the hole bottom 120 is preferably 60 μm or less, more preferably 50 μm or less, and particularly preferably 40 μm or less.

The edge 170 of the hole bottom 120 serves as a halo distance Wb, and the insulating layer 100 can be made parallel to the thickness direction of the insulating layer 100 and through the cross section of the center 120C of the hole bottom 120 by using FIB (Focused Ion Beam). After the method of cutting, the cross section was observed by an electron microscope and measured.

Further, according to the investigation by the inventors of the present invention, it has been found that the larger the diameter of the through hole 110 is, the larger the size of the halo portion 140 is. Therefore, the size of the gap portion 180 tends to be large. Thus, by the ratio of the size of the gap portion 180 to the diameter of the through hole 110, the degree of suppression of the halo phenomenon can be evaluated, and even the degree of suppression of the formation of the gap portion 180 can be evaluated. For example, it can be evaluated by the halo ratio Hb with respect to the bottom radius Lb/2 of the through hole 110. Here, the bottom radius Lb/2 of the through hole 110 refers to the radius of the hole bottom 120 of the through hole 110. Further, the halo ratio Hb with respect to the bottom radius Lb/2 of the through hole 110 is a ratio obtained by dividing the halo distance Wb from the edge 170 of the hole bottom 120 by the bottom radius Lt/2 of the through hole 110. The smaller the halo ratio Hb with respect to the bottom radius Lb/2 of the through hole 110, the more effectively the formation of the gap portion 180 can be suppressed.

For example, the insulating layer 100 obtained by heating the resin composition layer at 100 ° C for 30 minutes, and then heating at 180 ° C for 30 minutes, has a mask diameter of 1 mm, a pulse width of 16 μs, and an energy of 0.2 mJ/shot. In the case of the number 2 and the burst mode (10 kHz), the CO ₂ laser light was irradiated to form the via hole 110 having the top diameter Lt of 30 μm ± 2 μm. Thereafter, the mixture was immersed in a swelling solution at 60 ° C for 10 minutes, and then immersed in an oxidizing agent solution at 80 ° C for 20 minutes, followed by immersion in a neutralizing solution at 40 ° C for 5 minutes, followed by drying at 80 ° C for 15 minutes. In the case where such a roughening treatment is performed, the halo ratio Hb with respect to the bottom radius Lb/2 of the through hole 110 can be preferably 60% or less, more preferably 50% or less, and still more preferably 40. %the following.

The halo ratio Hb with respect to the bottom radius Lb/2 of the through hole 110 can be calculated from the bottom diameter Lb of the through hole 110 and the halo distance Wb from the edge 170 of the hole bottom 120 of the through hole 110.

In the manufacturing process of the printed wiring board, the through hole 110 is usually formed in a state in which the surface 100U of the insulating layer 100 on the opposite side of the conductor layer 210 is not provided with another conductor layer (not shown). Therefore, when the manufacturing process of the printed wiring board is known, it is possible to clearly recognize that the hole bottom 120 is on the side of the conductor layer 210 and that the hole top 130 has an opening on the side opposite to the conductor layer 210. However, in the completed printed wiring board, there may be a case where a conductor layer is provided on both sides of the insulating layer 100. In this case, it may be difficult to distinguish the hole bottom 120 from the hole top 130 due to the positional relationship with the conductor layer. However, generally, the top diameter Lt of the hole top 130 is greater than the bottom diameter Lb of the hole bottom 120. Thus, in the foregoing case, the hole bottom 120 and the hole top 130 can be distinguished by the diameter.

The inventors of the present invention estimated the structure obtained by the resin composition layer of the present invention as described above. However, the technical scope of the present invention is not limited by the configuration described below.

Generally, when the via hole 110 is formed, heat, light, or the like is applied to a portion of the via hole 110 where the insulating layer 100 is to be formed. A part of the energy imparted at this time may be transmitted to the periphery of the portion where the through hole 110 is to be formed, resulting in oxidation of the resin. If such oxidation occurs, the resin deteriorates and appears as a halo phenomenon. However, since the component (B) has an aromatic ring having two or more hydroxyl groups, the oxidative reaction of the resin can be suppressed by the steric hindrance of the hydroxyl group. Therefore, in the insulating layer 100 obtained by using the resin composition layer of the present invention, the halo phenomenon can be suppressed.

Further, as is known from the description of the average particle diameter and the specific surface area, the particle diameter of the component (C) contained in the resin composition layer is usually small. Since the particle diameter of the component (C) is small, the energy applied to the insulating layer 100 can be favorably transmitted to the thickness direction of the insulating layer 100. For example, when thermal energy or light energy is applied to the surface 100U of the insulating layer 100, the energy can be transmitted to the thickness direction without significant attenuation. Therefore, the through hole 110 having a large taper ratio can be easily formed, and therefore, the shape of the through hole 110 can be made good.

[11. Use of Resin Composition Layer] The resin composition layer of the present invention can be suitably used as a resin composition layer for insulation use. Specifically, the resin composition layer of the present invention can be suitably used as a resin composition layer (resin composition layer for forming an insulating layer of a printed wiring board) for forming an insulating layer of a printed wiring board, and further, it can be more suitably used. A resin composition layer (a resin composition layer for forming an interlayer insulating layer of a printed wiring board) to form an interlayer insulating layer of a printed wiring board is used. Further, the resin composition layer of the present invention can be suitably used as a resin composition layer for forming a conductive layer (including a rewiring layer) for forming the insulating layer (an insulating layer for forming a conductor layer) A resin composition layer).

In particular, the resin composition layer is suitable as a resin composition layer for forming an insulating layer having a through hole, from the viewpoint of effectively utilizing the advantage of suppressing the halo phenomenon and forming a good shape of the through hole. (Resin composition layer for forming an insulating layer having a through hole), and particularly suitable as a resin composition layer for forming an insulating layer having a through hole having a top diameter of 35 μm or less.

[12. Resin sheet] The resin sheet of the present invention comprises a support and a resin composition layer of the present invention provided on the support.

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 or a metal foil is preferable.

In the case of using a film made of a plastic material as a support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate ( Hereinafter, an acrylic polymer such as polyester, polycarbonate (hereinafter sometimes abbreviated as "PC") or polymethyl methacrylate (hereinafter sometimes abbreviated as "PMMA") may be simply referred to as "PEN" or the like. Cyclic polyolefin, triacetyl cellulose (hereinafter sometimes abbreviated as "TAC"), polyether sulfide (hereinafter sometimes abbreviated as "PES"), polyether ketone, polyimine, and the like. Among them, polyethylene terephthalate or polyethylene naphthalate is preferred, and polyethylene terephthalate which is preferably low in weight is preferred.

In the case of using a metal foil as a support, examples of the metal foil include a copper foil, an aluminum foil, and the like, and a copper foil is preferable. As the copper foil, a foil composed of a single metal of copper may be used, or a foil composed of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, hafnium, titanium, etc.) may be used. .

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

Further, as the support, a release layer support having a release layer on the surface joined to the resin composition layer may be used. The release agent used for the release layer to which the release layer support is attached may, for example, be selected from the group consisting of an alkyd resin, a polyolefin resin, a urethane resin, and a polyoxymethylene resin. One or more release agents. A commercially available product may be used as the release layer support, and for example, "SK-1" and "AL" manufactured by LINTEC Co., Ltd., which is a PET film having a release layer containing an alkyd-based release agent as a main component, may be used. -5", "AL-7"; "LUMIRROR T60" manufactured by Toray Co., Ltd.; "PUREX" manufactured by Teijin Co., Ltd.; "Unipeel" manufactured by Unitika Corporation.

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. Further, in the case where the release layer support is used, the thickness of the entire release layer support is preferably in the above range.

Further, the resin sheet may contain any layer other than the support and the resin composition layer as needed. For example, a protective film or the like which is provided as a support on the surface of the resin composition layer which is not bonded to the support (that is, the surface opposite to the support) may be mentioned. The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By protecting the film, adhesion or damage to dust or the like on the surface of the resin composition layer can be suppressed.

For the resin sheet, for example, a resin varnish containing an organic solvent and a resin composition can be prepared, and the resin varnish can be applied to a support by a coating device such as a die coater, and then dried to form a resin. The composition layer is made and manufactured.

Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, 赛 succinate, propylene glycol monomethyl ether acetate, and carbene. Acetate solvent such as alcohol acetate; carbitol solvent such as serosol and butyl carbitol; aromatic hydrocarbon solvent such as toluene and xylene; dimethylformamide, dimethylacetamidine A guanamine-based solvent such as an amine (DMAc) or N-methylpyrrolidone. The organic solvent may be used alone or in combination of two or more.

The drying can be carried out by heating, hot air blowing, or the like. The drying condition is not particularly limited, but the content of the organic solvent in the resin composition layer is usually 10% by mass or less, preferably 5% by mass or less. Although it varies depending on the boiling point of the organic solvent in the resin varnish, for example, when a resin varnish containing 30% by mass to 60% by mass of an organic solvent is used, it can be carried out at 50 ° C to 150 ° C for 3 minutes to 10 minutes. It is dried to form a resin composition layer.

The resin sheet can be stored by winding into a roll. In the case where the resin sheet has a protective film, it is usually in a usable state by peeling off the protective film.

[13. Printed wiring board] The printed wiring board of the present invention is provided with an insulating layer formed of a cured product of a resin composition layer as described above. Further, the insulating layer can suppress the halo phenomenon when the through hole is formed, and can form a through hole having a good shape. Therefore, by using the resin composition layer of the present invention, the thickness of the printed wiring board can be reduced while suppressing the deterioration of the performance due to the halo phenomenon or the deterioration of the shape of the through hole.

The through holes are usually provided to electrically connect the conductor layers provided on both sides of the insulating layer having the through holes. Therefore, the printed wiring board of the present invention usually includes a first conductor layer, a second conductor layer, and an insulating layer formed between the first conductor layer and the second conductor layer. Further, a through hole is formed in the insulating layer, and the first conductor layer and the second conductor layer can be electrically connected through the through hole.

By utilizing the advantage of the resin composition layer which can suppress the halo phenomenon and form a through hole of a good shape, it is possible to realize a specific printed wiring board which has been difficult to realize in the past. This specific printed wiring board includes a printed wiring board including a first conductor layer, a second conductor layer, and an insulating layer formed between the second conductors of the first conductor layer, and satisfies all of the following requirements (i) to (v). ). (i) The thickness of the insulating layer is 15 μm or less. (ii) The insulating layer has a through hole having a top diameter of 35 μm or less. (iii) The through hole has a taper ratio of 80% or more. (iv) The edge of the hole bottom of the through hole has a halo distance of 5 μm or less. (v) The halo ratio with respect to the bottom radius of the through hole is 35% or less.

Hereinafter, the drawings will be described, and a specific printed wiring board will be described. Fig. 4 is a schematic cross-sectional view showing a printed wiring board 300 according to a second embodiment of the present invention. In the fourth drawing, a cross section in which the printed wiring board 300 is cut is shown on a plane passing through the center 120C of the hole bottom 120 of the through hole 110 and parallel to the thickness direction of the insulating layer 100. Further, in the fourth drawing, the parts corresponding to the elements described in the first to third figures are denoted by the same reference numerals as those of the first to third figures.

As shown in FIG. 4, the specific printed wiring board 300 according to the second embodiment of the present invention includes the first conductor layer 210, the second conductor layer 220, and the first conductor layer 210 and the second conductor layer 220. Inter-insulating layer 100. A through hole 110 is formed in the insulating layer 100. Further, in general, the second conductor layer 220 is provided after the through holes 110 are formed. Therefore, the second conductor layer 220 is formed not only on the surface 100U of the insulating layer 100 but also in the via hole 110, and the first conductor layer 210 and the second conductor layer 220 are electrically connected through the via hole 110.

The thickness T of the insulating layer 100 included in the specific printed wiring board 300 is usually 15 μm or less, preferably 12 μm or less, more preferably 10 μm or less, and particularly preferably 5 μm or less. Since the specific printed wiring board 300 has such a thin insulating layer 100, the specific printed wiring board 300 can be made thinner by itself. The lower limit of the thickness T of the insulating layer 100 is preferably 1 μm or more, more preferably 2 μm or more, and particularly preferably 3 μm or more from the viewpoint of improving the insulating properties of the insulating layer 100. Here, the thickness T of the insulating layer 100 indicates the size of the insulating layer 100 between the first conductor layer 210 and the second conductor layer 220, and does not indicate the insulating layer at the position where the first conductor layer 210 or the second conductor layer 220 is absent. 100 size. The thickness T of the insulating layer 100 generally coincides with the distance between the main surface 210U of the first conductor layer 210 and the main surface 220D of the second conductor layer 220 facing the insulating layer 100, and the depth of the through hole 110. Consistent.

The top diameter Lt of the through hole 110 included in the insulating layer 100 included in the specific printed wiring board 300 is usually 35 μm or less, preferably 33 μm or less, and particularly preferably 32 μm or less. Since the specific printed wiring board 300 includes the insulating layer 100 having the through holes 110 having a small top diameter Lt as described above, it is possible to promote the miniaturization of the wiring including the first conductor layer 210 and the second conductor layer 220. The lower limit of the top diameter Lt of the through hole 110 is preferably 3 μm or more, more preferably 10 μm or more, and particularly preferably 15 μm or more from the viewpoint of facilitating the formation of the through hole 110.

The taper ratio Lb/Lt (%) of the through hole 110 included in the insulating layer 100 included in the specific printed wiring board 300 is usually 80% to 100%. The specific printed wiring board 300 is an insulating layer 100 including the through holes 110 having a good shape with a tapered ratio Lb/Lt. Therefore, the specific printed wiring board 300 can generally improve the reliability of conduction between the first conductor layer 210 and the second conductor layer 220.

The edge 170 of the hole bottom 120 of the through hole 110 included in the insulating layer 100 included in the specific printed wiring board 300 has a halo distance Wb of usually 5 μm or less, preferably 4 μm or less. Since the edge 170 of the specific printed wiring board 300 by the hole bottom 120 has such a small halo distance Wb, the peeling from the insulating layer 100 of the first conductor layer 210 is small. Therefore, the specific printed wiring board 300 can generally improve the reliability of conduction between the first conductor layer 210 and the second conductor layer 220.

The halo ratio Hb of the insulating layer 100 included in the specific printed wiring board 300 with respect to the bottom radius Lb/2 of the through hole 110 is usually 35% or less, preferably 33% or less, more preferably 31% or less. . Since the specific printed wiring board 300 is so small in the halo ratio Hb with respect to the bottom radius Lb/2, the peeling from the insulating layer 100 of the first conductor layer 210 is small. The specific printed wiring board 300 including the insulating layer 100 having a smaller halo than Hb generally improves the reliability of conduction between the first conductor layer 210 and the second conductor layer 220. The lower limit of the halo ratio Hb with respect to the bottom radius Lb/2 is desirably zero, but is usually 5% or more.

The number of the through holes 110 included in the insulating layer 100 included in the specific printed wiring board 300 may be one or two or more. In the case where the insulating layer 100 has two or more through holes 110, some of them may satisfy the requirements (ii) to (v), but preferably all of them satisfy the requirements (ii) to (v). Further, for example, it is preferable that the through holes 110 of the five portions randomly selected by the insulating layer 100 satisfy the requirements (ii) to (v) on average.

The specific printed wiring board 300 described above can be realized by forming the insulating layer 100 by the cured product of the resin composition layer of the present invention. At this time, although the planar shape of the hole bottom 120 and the hole top 130 formed in the through hole 110 of the insulating layer 100 is arbitrary, it is generally a circular shape or an elliptical shape, and is preferably a circular shape.

A printed wiring board such as a specific printed wiring board can be produced, for example, by using a resin sheet to carry out the production method including the following steps (I) to (III). (I) A step of laminating a resin sheet on the inner substrate so that the resin composition layer and the inner layer substrate are joined to each other. (II) a step of thermally curing the resin composition layer to form an insulating layer. (III) a step of forming a via hole in the insulating layer.

The "inner substrate" used in the step (I) means a member that becomes a substrate of the printed wiring board. Examples of the inner layer substrate include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. Usually, the inner layer substrate is used for a conductor layer having one or both sides. Next, an insulating layer is formed on the conductor layer. This conductor layer can be patterned, for example, in order to function as a circuit. An inner layer substrate in which a conductor layer is formed as a circuit on one side or both sides of a substrate may be referred to as an "inner layer circuit board". Further, in the production of a printed wiring board, an intermediate product for further forming an insulating layer and/or a conductor layer is also included in the "inner substrate". In the case where the printed wiring board is a circuit board in which the components are built, an inner substrate in which the components are mounted may be used.

The inner layer substrate and the resin sheet are laminated, and for example, the resin sheet can be bonded to the inner layer substrate by heating and pressure-bonding the resin sheet from the support side to the inner layer substrate. The member for heating and pressure-bonding the resin sheet to the inner layer substrate (hereinafter referred to as "heating pressure bonding member") may, for example, be a heated metal plate (such as a SUS mirror plate) or a metal roll (SUS roll). . In addition, it is preferable to pressurize the heating pressure-bonding member directly to the resin sheet, and to pressurize the resin sheet so as to sufficiently follow the surface unevenness of the inner layer substrate via an elastic material such as heat-resistant rubber.

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

The lamination system can be carried out by a commercially available vacuum laminator. For example, a vacuum press type laminator manufactured by Nippon Seisakusho Co., Ltd., a Vacuum Applicator manufactured by Nikko-Materials Co., Ltd., a batch type vacuum press lamination machine, or the like can be given.

After the lamination, under normal pressure (at atmospheric pressure), for example, the heated resin member may be subjected to a smoothing treatment by laminating the heated pressure-bonding member from the side of the support. The pressurization conditions of the smoothing treatment can be set to the same conditions as the above-described laminated thermal pressure bonding conditions. The smoothing treatment can be carried out by a commercially available laminator. Further, the lamination and smoothing treatment can be continuously performed using the commercially available vacuum laminator described above.

In the step (II), the resin composition layer is thermally hardened to form an insulating layer. The thermosetting condition of the resin composition layer is not particularly limited, and the conditions used in forming the insulating layer of the printed wiring board can be arbitrarily used.

For example, the thermosetting conditions of the resin composition layer vary depending on the type of the resin composition, etc., but the curing temperature is usually in the range of 120 ° C to 240 ° C (preferably in the range of 150 ° C to 220 ° C, more preferably The curing time is usually in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 minutes).

The resin composition layer may be preheated at a temperature lower than the curing temperature before the resin composition layer is thermally cured. For example, the resin may be firstly heated at a temperature of usually 50 ° C or more and less than 120 ° C (preferably 60 ° C or more and 115 ° C or less, more preferably 70 ° C or more and 110 ° C or less) before the resin composition layer is thermally cured. The composition layer is subjected to preliminary heating for usually 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, still more preferably 15 minutes to 100 minutes).

In the step (III), a through hole is formed in the insulating layer. Examples of the method of forming the through holes include irradiation of laser light, etching, mechanical drilling, and the like. Among them, the irradiation of laser light is generally prone to halo phenomenon. Therefore, from the viewpoint of effectively utilizing the effect of suppressing the halo phenomenon, it is preferable to irradiate the laser light.

The irradiation of the laser light can be performed, for example, using a laser processing machine having a laser light source such as a carbon dioxide laser, a YAG laser, or a quasi-molecular laser as a light source. Examples of the laser processing machine that can be used include a CO ₂ laser processing machine "LC-2k212/2C" manufactured by Via Mechanics, a 605GTWIII (-P) manufactured by Mitsubishi Electric Corporation, and a mine manufactured by Panasonic Welding Systems. Injection processing machine, etc.

The irradiation conditions of the laser light such as the wavelength of the laser light, the number of pulses, the pulse width, and the output are not particularly limited, and an appropriate condition depending on the type of the laser light source may be set.

In addition, the support may be removed between step (I) and step (II), may be removed between step (II) and step (III), or may be removed after step (III). Among them, from the viewpoint of further suppressing the occurrence of the cut portion, it is preferably removed after the step (III) of forming the through hole in the insulating layer. For example, if the support is peeled off after the through holes are formed in the insulating layer by the irradiation of the laser light, it is easy to form a through hole having a good shape.

The method for producing a printed wiring board may further include (IV) a step of roughening the insulating layer and (V) a step of forming a conductor layer. These steps (IV) and (V) can also be carried out in accordance with various methods used in the manufacture of printed wiring boards. In addition, in the case where the support is removed after the step (III), the removal of the support may be performed between the step (III) and the step (IV), or may be performed in the steps (IV) and (V). Implementation.

Step (IV) is a step of roughening the insulating layer. The procedure and conditions of the roughening treatment are not particularly limited, and any procedures and conditions used in forming the insulating layer of the printed wiring board can be employed. For example, the insulating layer may be subjected to a roughening treatment by sequentially performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid.

The swelling solution is not particularly limited, and examples thereof include an alkali solution and a surfactant solution, and an alkali solution is preferred. As the alkali solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferred. As a commercially available swelling liquid, for example, "Swelling Dip Securiganth P" manufactured by Atotech Japan Co., Ltd., "Swelling Dip Securiganth SBU", and the like can be mentioned. Further, the swelling liquid may be used singly or in combination of two or more kinds in any ratio. The swelling treatment by the swelling liquid is not particularly limited, and for example, it can be carried out by immersing the insulating layer in a 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 preferred to immerse the insulating layer in a swelling liquid at 40 ° C to 80 ° C for 5 minutes to 15 minutes.

The oxidizing agent is not particularly limited, and examples thereof include an alkaline permanganic acid solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. Further, the oxidizing agent may be used singly or in combination of two or more kinds in any ratio. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated to 60 ° C to 80 ° C for 10 minutes to 30 minutes. Further, the concentration of the permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. The commercially available oxidizing agent may, for example, be an alkaline permanganic acid solution such as "Concentrate Compact CP" manufactured by Atotech Japan Co., Ltd. or "Dosing Solution Securiganth P".

The neutralization liquid is preferably an acidic aqueous solution, and a commercially available product is, for example, "Reduction solution Securiganth P" manufactured by Atotech Japan Co., Ltd. Further, the neutralizing liquid system may be used singly or in combination of two or more kinds in any ratio. The treatment with the neutralizing solution can be carried out by immersing the treated surface subjected to the roughening treatment with an oxidizing agent in 30 ° C to 80 ° C and in the liquid for 5 minutes to 30 minutes. In terms of workability and the like, a method in which the object subjected to the roughening treatment with an oxidizing agent is immersed in a temperature of 40 to 70 ° C and a liquid for 5 minutes to 20 minutes is preferred.

Step (V) is a step of forming a conductor layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer comprises one selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The above metal. The conductor layer may be a single metal layer or an alloy layer. The alloy layer may, for example, be a layer formed of an alloy (for example, a nickel/chromium alloy, a copper/nickel alloy, a copper or a titanium alloy) selected from two or more metals selected from the above group. Among them, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper is preferred from the viewpoints of versatility of the formation of the conductor layer, cost, ease of patterning, and the like; Or an alloy layer of nickel, chromium alloy, copper, nickel alloy, copper or titanium alloy. Further, it is more preferably a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper; or an alloy layer of nickel/chromium alloy, particularly preferably a single metal layer of copper.

The conductor layer may have a single layer structure or a multilayer structure including two or more single metal layers or alloy layers composed of different kinds of metals or alloys. In the case where the conductor layer has a multilayer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium or an alloy layer of nickel/chromium alloy.

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

The conductor layer can also be formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating on the surface of the insulating layer by a technique such as a semi-additive method or a full additive method. Among them, from the viewpoint of the simplicity of production, it is preferably formed by a semi-additive method.

Hereinafter, an example in which a conductor layer is formed by a semi-additive method is shown. First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, on the formed plating seed layer, a mask pattern in which a part of the plating seed layer is exposed corresponding to the desired wiring pattern is formed. After the metal layer is formed by electrolytic plating on the exposed plated seed layer, the mask pattern is removed. Thereafter, the unnecessary plating seed layer is removed by etching or the like to form a conductor layer having a desired wiring pattern.

First, a multilayer printed wiring board can be manufactured by repeatedly performing the formation of the insulating layer and the conductor layer by the steps (I) to (V) as needed.

[14. Semiconductor device] The semiconductor device of the present invention includes the above-described printed wiring board. This semiconductor device can be fabricated using a printed wiring board.

Examples of the semiconductor device include various semiconductor devices that are supplied to electrical products (for example, computers, mobile phones, digital cameras, and televisions) and vehicles (for example, locomotives, automobiles, electric cars, ships, and aircrafts).

The semiconductor device can be manufactured, for example, by mounting a component (semiconductor wafer) on a conductive portion of the printed wiring board. The "conduction portion" is "the portion where the electrical signal is transmitted on the printed wiring board", and the location may be either a surface or a buried portion. Further, the semiconductor wafer can be arbitrarily used as a circuit element using a semiconductor as a material.

The method of mounting the semiconductor wafer in the manufacture of the semiconductor device is not particularly limited as long as the semiconductor wafer can function effectively. Examples of the mounting method include a wire bonding mounting method, a flip chip mounting method, a flangeless build-up layer (BBUL) mounting method, an anisotropic conductive film (ACF) mounting method, and a non-conductive film (NCF). ) Installation method, etc. Here, the "mounting method of the flangeless build-up layer (BBUL)" means a "mounting method of directly attaching a semiconductor wafer to a concave portion of a printed wiring board and connecting the semiconductor wafer to the wiring on the printed wiring board". [Examples]

Hereinafter, the embodiments of the present invention will be specifically described. However, the invention is not limited to the following examples. In the following description, "parts" and "%" of the quantity mean "parts by mass" and "% by mass" unless otherwise stated. Further, the operation described below is carried out in an environment of normal temperature and normal pressure unless otherwise specified.

[Description of Inorganic Filler] <Method for Measuring Average Particle Diameter of Inorganic Filler> 100 mg of the inorganic filler, 0.1 g of a dispersant ("SN9228" manufactured by SAN NOPCO Co., Ltd.), and 10 g of methyl ethyl ketone were weighed in the medicine. In the bottle, it was dispersed by ultrasonic for 20 minutes. The particle size distribution of the inorganic filler was measured by a batch processing unit using a laser diffraction type particle size distribution measuring apparatus ("SALD-2200" manufactured by Shimadzu Corporation) on a volume basis. Next, the average particle diameter of the inorganic filler was calculated from the obtained particle diameter distribution as the median diameter.

<Method for Measuring 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.).

<Type of Inorganic Filler> Inorganic Filler 1: 100 parts of spherical cerium oxide ("UFP-30", average particle diameter: 0.078 μm, specific surface area: 30.7 m ² /g, manufactured by Denki Kagaku Kogyo Co., Ltd.), N- Phenyl-3-aminopropyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM573) was subjected to surface treatment in two parts.

Inorganic filler 2: 100 parts of spherical cerium oxide ("SC2500SQ" manufactured by Admatech Co., Ltd., average particle diameter 0.77 μm, specific surface area 5.9 m ² /g), and N-phenyl-3-aminopropyltrimethoxy One part of decane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM573) was subjected to surface treatment.

[Example 1. Preparation of Resin Composition 1] 6 parts of a bixylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 185), and a naphthalene type epoxy resin (Nippon Steel & Sumitomo Chemical Co., Ltd. Company made "ESN475V", epoxy equivalent of about 332) 5 parts, bisphenol AF type epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 238) 15 parts, cyclohexane type epoxy resin (Mitsubishi Chemical Company's "ZX1658GS", epoxy equivalent of about 135) 2 parts, and phenoxy resin ("XX7553BH30" by Mitsubishi Chemical Corporation, 30% by mass of cyclohexanone: methyl ethyl ketone (MEK)) Two parts of a 1:1 solution and Mw = 35000) were heated and dissolved in a mixed solvent of 20 parts of a solvent naphtha and 10 parts of cyclohexanone while stirring. The resulting solution was cooled to room temperature. Then, a naphthol-based curing agent (the aromatic hydrocarbon resin represented by the formula (5). "SN395" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., hydroxyl equivalent 107) 5 was mixed in the solution. A portion, an active ester-based curing agent ("EXB-8000L-65TM" manufactured by DIC Corporation, a reactive base equivalent of about 220, a non-volatile component of 65 mass% of toluene: a 1:1 solution of MEK), 6 parts, and an inorganic filler 1 50. A part and an amine-based hardening accelerator (4-dimethylaminopyridine (DMAP)) were 0.05 parts, and uniformly dispersed in a high-speed rotary mixer to obtain a mixture. This mixture was filtered with a cartridge filter ("SHP020" manufactured by ROKITECHNO Co., Ltd.) to obtain a resin composition 1.

[Example 2: Preparation of Resin Composition 2] The resin composition 2 was prepared in the same manner as in Example 1 except that the type and amount of the reagent to be used were changed as shown in Table 1. The specific changes from the first embodiment are as follows. In place of the cyclohexane type epoxy resin ("ZX1658GS" manufactured by Mitsubishi Chemical Corporation, and an epoxy equivalent of about 135), two parts were used, and a bisphenol type epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., epoxy equivalent) was used. 169, 1:1 mixture of bisphenol A type and bisphenol F type) 4 parts, and stretching naphthyl ether type epoxy resin ("EXA-7311-G4" by DIC company, epoxy equivalent of about 213) 2 parts . Further, a phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, a non-volatile component of 30% by mass of cyclohexanone: a methyl ketone (MEK) 1:1 solution, Mw = 35000) was used, and A phenoxy resin ("YL7500BH30" manufactured by Mitsubishi Chemical Corporation, a non-volatile component of 30% by mass of cyclohexanone: a methyl ketone (MEK) 1:1 solution, Mw = 44000) was used. Further, as the component (B), a naphthol-based curing agent ("SN395" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., and a hydroxyl group equivalent of 107) was substituted for 5 parts, and a phenol-based curing agent (aromatic represented by the formula (4)) was used. Hydrocarbon resin: "GRA13H" manufactured by Kyoei Chemical Industry Co., Ltd., having a hydroxyl equivalent of about 75).

[Comparative Example 1. Preparation of Resin Composition 3] The resin composition 3 was prepared in the same manner as in Example 1 except that the type and amount of the reagent to be used were changed as shown in Table 1. The specific changes from the first embodiment are as follows. In place of the cyclohexane type epoxy resin ("ZX1658GS" manufactured by Mitsubishi Chemical Corporation, and an epoxy equivalent of about 135), two parts were used, and a bisphenol type epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., epoxy equivalent) was used. 169, 1:1 mixture of bisphenol A type and bisphenol F type) 4 parts, and stretching naphthyl ether type epoxy resin ("EXA-7311-G4" by DIC company, epoxy equivalent of about 213) 2 parts . Further, a phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, a non-volatile component of 30% by mass of cyclohexanone: a methyl ketone (MEK) 1:1 solution, Mw = 35000) was used, and A phenoxy resin ("YL7500BH30" manufactured by Mitsubishi Chemical Corporation, a non-volatile component of 30% by mass of cyclohexanone: a methyl ketone (MEK) 1:1 solution, Mw = 44000) was used. Further, in place of a naphthol-based curing agent ("SN395" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., and a hydroxyl group equivalent of 107), 5 parts of a cresol novolak-based hardener (DIC) containing a triazine skeleton as the component (E) was used. 10 parts of "LA-3018-50P", a hydroxyl equivalent of about 151, and a 50% non-volatile component of 2-methoxypropanol solution).

[Comparative Example 2. Preparation of Resin Composition 4] The resin composition 4 was prepared in the same manner as in Example 1 except that the type and amount of the reagent to be used were changed as shown in Table 1. The specific changes from the first embodiment are as follows. In place of a naphthol-based curing agent ("SN395" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., and a hydroxyl group equivalent of 107), 5 parts of a cresol novolak-based hardener containing a triazine skeleton as the component (E) (manufactured by DIC Corporation) 4 parts of LA-3018-50P", a hydroxyl equivalent of about 151, and a 50% non-volatile component of 2-methoxypropanol). Further, in place of 50 parts of the inorganic filler, 80 parts of the inorganic filler was used.

[Comparative Example 3: Preparation of Resin Composition 5] The resin composition 5 was prepared in the same manner as in Example 1 except that the type and amount of the reagent to be used were changed as shown in Table 1. The specific changes from the first embodiment are as follows. A naphthol-based curing agent ("SN395" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., and a hydroxyl group equivalent of 107) was used as a substitute, and a naphthol-based curing agent (SN485, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) was used. A cresol novolak-based curing agent having a hydroxyl group equivalent of about 215) and a triazine skeleton ("LA-3018-50P" manufactured by DIC Corporation, a 2-hydroxy group having a hydroxyl equivalent of about 151 and a nonvolatile component of 50%). Propanol solution) 4 parts.

[Comparative Example 4: Preparation of Resin Composition 6] The resin composition 6 was prepared by the same operation as in Example 1 except that the type and amount of the reagent to be used were changed as shown in Table 1. The specific changes from the first embodiment are as follows. As a curing agent, a combination of a naphthol curing agent ("SN395" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., hydroxyl equivalent 107) and 5 parts of an active ester-based curing agent (EXB-8000L-65TM manufactured by DIC Corporation) and an active base equivalent are used. 220, 6 parts by mass of a non-volatile component of 65% by mass of toluene: 1:1 solution of MEK, and further, a cresol novolak-based hardener containing a triazine skeleton as the component (E) (LA-made by DIC Corporation) 4 parts of 3018-50P", a hydroxyl equivalent of about 151, and a 50% non-volatile component of 2-methoxypropanol). Further, in place of 150 parts of the inorganic filler, 80 parts of the inorganic filler was used.

[Composition of Resin Composition] The components used in the preparation of the resin compositions 1 to 6 and the blending amount thereof (parts by mass of the nonvolatile components) are shown in Table 1 below. The abbreviations in the following tables are as follows. The content of the hardener: the content of the hardener relative to 100% by mass of the resin component in the resin composition. The content of the active ester-based curing agent is the content of the active ester-based curing agent relative to 100% by mass of the resin component in the resin composition. The content of the inorganic filler: the content of the inorganic filler relative to 100% by mass of the nonvolatile component in the resin composition.

[Production of Resin Sheet] A polyethylene terephthalate film ("LUMIRROR R80" manufactured by Toray Co., Ltd.) was prepared as a support system by a release treatment using an alkyd resin release agent ("AL-5" manufactured by LINTEC Co., Ltd.). , thickness 38 μm, softening point 130 ° C).

Each of the resin compositions 1 to 6 was uniformly applied to a support by a die coater so that the thickness of the dried resin composition layer was 10 μm, and dried at 70 ° C for 2 minutes at 95 ° C. Thus, a resin composition layer is formed on the support. Then, on the surface of the resin composition layer which was not bonded to the support, the rough surface of the polypropylene film ("Alphan MA-411" manufactured by Oji F-Tex Co., Ltd., thickness: 15 μm) of the protective film was bonded. Thereby, the resin sheet A which has a support body, a resin composition layer, and a protective film in order is obtained.

[Measurement Method of Thickness] The thickness of the layer of the resin composition layer or the like was measured using a contact type film thickness meter ("MCD-25MJ" manufactured by Mitutoyo Co., Ltd.).

[Evaluation of Through Holes After Laser Drilling] Using the resin sheet A produced by each of the resin compositions 1 to 6, an insulating layer having through holes is formed by the following method, and the through holes are formed. Evaluation.

<Preparation of sample for evaluation> (1) Preparation of inner layer substrate: As an inner layer substrate, a glass cloth substrate having a copper foil layer on both sides was prepared, and a copper laminate was bonded on both sides (the thickness of the copper foil was 3 μm, and the thickness of the substrate was 0.15). Mm, "HL832NSF LCA" manufactured by Mitsubishi Gas Chemical Co., Ltd., 255 x 340 mm size).

(2) Lamination of Resin Sheet: The protective film is peeled off from the resin sheet A to expose the resin composition layer. A batch type vacuum press laminator (a two-stage stacking machine "CVP700" manufactured by Nikko-Materials Co., Ltd.) was used to laminate the resin composition layer on both sides of the inner substrate so as to be in contact with the inner layer substrate. Floor. The lamination was carried out by adjusting the gas pressure to 13 hPa or less after performing pressure reduction for 30 seconds, and then performing pressure bonding at 130 ° C and a pressure of 0.74 MPa for 45 seconds. Next, hot pressing was performed for 75 seconds at 120 ° C and a pressure of 0.5 MPa.

(3) Thermal hardening of the resin composition layer: Thereafter, the inner substrate on which the resin sheet was laminated was placed in an oven at 100 ° C for 30 minutes, and then transferred to an oven at 180 ° C for 30 minutes to heat the resin. The layer is thermally hardened to form an insulating layer. The thickness of the insulating layer was 10 μm. Thereby, a hardened substrate A having a support, an insulating layer, an inner layer substrate, an insulating layer, and a support in this order is obtained.

(4) Laser drilling: Using a CO ₂ laser processing machine ("GTGTWIII (-P)" manufactured by Mitsubishi Electric Corporation), the insulating layer is irradiated with laser light through a support, and a top diameter (diameter) is formed in the insulating layer. ) is a plurality of through holes of about 30 μm. The irradiation conditions of the laser light are a mask diameter of 1 mm, a pulse width of 16 μs, an energy of 0.2 mJ/shot, a shot number of 2, and a burst mode (10 kHz).

(5) Roughening treatment: After the through holes are formed in the insulating layer, the support is peeled off to obtain a drilled substrate A having an insulating layer, an inner substrate, and an insulating layer in this order. Thereafter, the substrate A is drilled and subjected to a desmearing treatment as a roughening treatment. The following desmear treatment was carried out as a desmear treatment system.

(Wet degreasing treatment) The drilled substrate A was immersed in a swelling liquid ("Swelling Dip Securiganth P" manufactured by Atotech Japan Co., Ltd., an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60 ° C. In the next, the solution was immersed in an oxidizing agent solution (Concentrate Compact CP, manufactured by Atotech Japan Co., Ltd., an aqueous solution having a potassium permanganate concentration of about 6% and a sodium hydroxide concentration of about 4%) at 80 ° C for 20 minutes, followed by 40 ° C. After immersing in a neutralizing liquid ("Reduction solution Securiganth P" manufactured by Atotech Japan Co., Ltd., aqueous sulfuric acid solution) for 5 minutes, it was dried at 80 ° C for 15 minutes. The drilled substrate A subjected to the wet desmearing treatment is referred to as a roughened substrate A.

<Measurement of the size of the through hole before the roughening treatment> The drilled substrate A before the roughening treatment is prepared as the sample system. For the drilled substrate A, a cross-sectional observation was performed using a FIB-SEM composite device ("SMI3050SE" manufactured by SII NanoTechnology Co., Ltd.). Specifically, the FIB (Focused Ion Beam) is used to cut the insulating layer so as to appear parallel to the thickness direction of the insulating layer and through the cross section of the center of the hole bottom of the through hole. The cross section was observed by SEM (scanning electron microscope), and the top and bottom diameters of the through holes were measured from the observed images.

The above measurement was carried out in the through holes of the five selected portions. Further, the average of the measured values of the top diameters of the through holes of the five portions measured was taken as the top diameter Lt1 of the through holes of the sample. Further, the average of the measured values of the bottom diameters of the through holes measured at the five locations was taken as the bottom diameter Lb1 of the through holes of the sample.

<Measurement of Size of Through Hole After Roughening Process> The roughened substrate A is used as a sample system instead of the drilled substrate A. In addition to the above, the same operation as the above-described <Measurement of the size of the through hole before the roughening treatment> was performed, and the top diameter Lt2 and the bottom diameter Lb2 of the through hole after the roughening treatment were measured.

<Measurement of the halo distance before the roughening treatment> The drilled substrate A before the roughening treatment was observed with an optical microscope ("KH8700" manufactured by Hirox Co., Ltd.). Specifically, an insulating layer around the through hole is observed from the upper portion of the drilled substrate A using an optical microscope (CCD). This observation is performed by aligning the focus of the optical microscope with the through holes. As a result of the observation, around the through hole, it was observed that the insulating layer became a white donut-shaped halo portion continuously from the edge of the hole top of the through hole. Therefore, from the observed image, the radius of the hole top of the through hole (corresponding to the inner circumference radius of the halo portion) r1, and the outer radius r2 of the halo portion, and the difference r2 between the radius r1 and the radius r2 are measured. R1 was calculated as the halo distance from the edge of the hole top of the measurement site.

The above measurement was carried out using through-holes of five sites randomly selected. Further, the average of the measured values of the halo distances of the through holes of the five portions measured was used as the halo distance Wt from the edge of the hole top of the sample.

<Measurement of the size of the halo distance after the roughening treatment> The cross-sectional observation was performed on the roughened substrate A using a FIB-SEM composite apparatus ("SMI3050SE" manufactured by SII NanoTechnology Co., Ltd.). Specifically, the FIB (Focused Ion Beam) is used to cut the insulating layer so as to appear parallel to the thickness direction of the insulating layer and through the cross section of the center of the hole bottom of the through hole. This section was observed by SEM (Scanning Electron Microscope). As a result of the observation, it was observed that the gap formed by the insulating layer from the copper foil layer of the inner substrate continued from the edge of the bottom of the hole. From the observed image, the distance from the center of the bottom of the hole to the edge of the bottom of the hole (corresponding to the inner peripheral radius of the halo portion) r3, and the distance from the center of the bottom of the hole to the end portion away from the gap portion side ( Corresponding to the outer radius of the halo portion, r4, the difference r4-r3 between the distance r3 and the distance r4 is calculated as the halo distance from the edge of the bottom of the measurement site.

The above measurement was carried out using through-holes of five sites randomly selected. Further, the average of the measured values of the halo distances of the through holes measured at the five locations was used as the halo distance Wb from the edge of the bottom of the sample.

[Results] The evaluation results of the foregoing examples and comparative examples are shown in Table 2 below. In Table 2, the taper ratio indicates the ratio "Lb1/Lt1" of the top diameter Lt1 and the bottom diameter Lb1 of the through hole before the roughening treatment. When the taper ratio Lb1/Lt1 is 75% or more, the drilling processability is judged as "good", and if the taper ratio Lb1/Lt1 is less than 75%, the drilling processability is judged as "poor". .

In Table 2, the halo ratio Ht before the roughening treatment indicates the halo distance Wt from the edge of the hole top before the roughening treatment, and the radius of the hole top of the through hole before the roughening treatment (Lt1/2) The ratio is "Wt/(Lt1/2)". If the halo ratio Ht is 35% or less, the halo evaluation is judged as "good", and if the halo ratio Ht is greater than 35%, the halo evaluation is judged as "poor".

In Table 2, the halo ratio Hb after the roughening treatment indicates the halo distance Wb from the edge of the bottom of the hole after the roughening treatment, and the radius of the bottom of the through hole after the roughening treatment (Lb2/2). The ratio is "Wb/(Lb2/2)". If the halo ratio Hb is 35% or less, the halo evaluation is judged as "good", and if the halo ratio Ht is more than 35%, the halo evaluation is judged as "poor".

[Discussion] As is apparent from Table 2, in the embodiment, since the insulating layer is formed using a thin resin composition layer having a thickness of 10 μm, a through hole having a large taper ratio can be formed in the insulating layer. As a result, it was confirmed that the resin composition layer of the present invention can realize an insulating layer which can form a through hole having a good shape even if the thickness is small.

Further, as is known from Table 2, in the embodiment, a thin resin composition layer having a thickness of 10 μm was used to form an insulating layer, and the halo ratio of the halo portion generated along with the formation of the through holes was small. As a result, it was confirmed that the insulating layer of the resin composition layer of the present invention can suppress the halo phenomenon even if the thickness is small.

In particular, the thickness is 15 μm or less, the top diameter of the via hole is 35 μm or less, the taper ratio of the via hole is 80% or more, and the halo distance of the bottom of the via hole is 5 μm as obtained in the above Examples 1 and 2. Hereinafter, an insulating layer having a halo ratio of 35% or less with respect to the bottom radius of the through hole has not been conventionally realized. Therefore, the realization of such an insulating layer has a significant technical significance in the recent development of a printed wiring board in which the thickness of the insulating layer is reduced.

In the first to second embodiments, although the specific results of the case where the conductor layer is formed on the insulating layer of the roughened substrate A are not shown, if the result of the above embodiment is observed, the substrate of the substrate A is roughened by roughening. The formation of the conductor layer to obtain a specific printed wiring board that satisfies the requirements (i) to (v) can be clearly understood by the industry. Further, in Examples 1 and 2, it was confirmed that even when the components (D) to (F) were not contained, the results were the same as those of the above examples.

100‧‧‧Insulation

100U‧‧‧face of the insulating layer on the opposite side of the conductor layer

110‧‧‧through hole

120‧‧‧ hole bottom

120C‧‧‧ Center of the hole bottom

130‧‧‧ hole top

140‧‧‧Hammer

150‧‧‧The edge of the hole top of the through hole

160‧‧‧ Edge of the outer peripheral side of the halo

170‧‧‧ Edge of the bottom of the hole

180‧‧‧ gap section

190‧‧‧End of the outer side of the gap

200‧‧‧ Inner substrate

210‧‧‧Conductor layer (1st conductor layer)

220‧‧‧2nd conductor layer

300‧‧‧Printed wiring board

Lb‧‧‧ hole diameter

Top diameter of Lt‧‧‧ through hole

T‧‧‧ thickness of insulation

The halo distance from the edge of the Wt‧‧ hole top

The halo distance from the edge of the Wb‧‧ hole bottom

[Fig. 1] Fig. 1 is a cross-sectional view schematically showing an insulating layer and an inner layer substrate obtained by curing the resin composition layer of the first embodiment of the present invention. [Fig. 2] Fig. 2 is a plan view schematically showing a surface of the insulating layer obtained by curing the resin composition layer of the first embodiment of the present invention on the opposite side to the conductor layer. [Fig. 3] Fig. 3 is a cross-sectional view showing the insulating layer and the inner layer substrate after the roughening treatment obtained by curing the resin composition layer of the first embodiment of the present invention. Fig. 4 is a schematic cross-sectional view showing a printed wiring board according to a second embodiment of the present invention.

Claims (14)

A resin composition layer comprising a resin composition layer having a thickness of 15 μm or less of a resin composition, wherein the resin composition comprises (A) an epoxy resin and (B) a monocyclic or condensed ring having two or more hydroxyl groups. The aromatic hydrocarbon resin of the aromatic ring and (C) an inorganic filler having an average particle diameter of 100 nm or less. A resin composition layer comprising a resin composition layer having a thickness of 15 μm or less of a resin composition, wherein the resin composition comprises (A) an epoxy resin and (B) a monocyclic or condensed ring having two or more hydroxyl groups. The aromatic hydrocarbon resin of the aromatic ring and (C) an inorganic filler having a specific surface area of 15 m ² /g or more. The resin composition layer of claim 1 or 2, wherein the component (B) is represented by the following formula (1) or formula (2): (In the formula (1), R ⁰ each independently represents a divalent hydrocarbon group, and n1 represents an integer of 0 to 6), (In the formula (2), R ¹ to R ⁴ each independently represent a hydrogen atom or a monovalent hydrocarbon group). The resin composition layer of claim 1 or 2, wherein the component (B) is represented by the following formula (3) or formula (4): (in equation (3), n2 represents an integer from 0 to 6), (In the formula (4), R ¹ to R ⁴ each independently represent a hydrogen atom or a monovalent hydrocarbon group). The resin composition layer of claim 1 or 2, wherein the amount of the component (B) is from 5% by mass to 50% by mass based on 100% by mass of the resin component in the resin composition. The resin composition layer of claim 1 or 2, wherein the amount of the component (C) is 50% by mass or more based on 100% by mass of the nonvolatile component in the resin composition. The resin composition layer of claim 1 or 2 for forming an insulating layer for forming a conductor layer. The resin composition layer of claim 1 or 2, which is used for forming an interlayer insulating layer of a printed wiring board. The resin composition layer of claim 1 or 2, which is formed of an insulating layer having a through hole having a top diameter of 35 μm or less. A resin sheet comprising a support and a resin composition layer according to any one of claims 1 to 9 which is provided on the support. A printed wiring board comprising an insulating layer formed of a cured product of the resin composition layer according to any one of claims 1 to 9. A printed wiring board comprising a first conductor layer, a second conductor layer, and a printed wiring board formed of an insulating layer between the first conductor layer and the second conductor layer, wherein the insulating layer has a thickness of 15 μm or less, and the insulating layer a through hole having a top diameter of 35 μm or less, the through hole having a taper ratio of 80% or more, a bottom of the through hole having a halo distance of 5 μm or less, and a halo ratio relative to a bottom radius of the through hole ( The halo ratio is 35% or less. The printed wiring board of claim 12, wherein the halo ratio with respect to the bottom radius of the through hole is 5% or more. A semiconductor device comprising the printed wiring board according to any one of claims 11 to 13.