KR20180123985A - 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 μm 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 m^2/g.

Description

Resin composition layer {RESIN COMPOSITION LAYER}

The present invention relates to a resin composition layer. The present invention also provides a resin sheet comprising the resin composition layer; And an insulating layer formed of a cured product of the resin composition layer.

In recent years, in order to achieve miniaturization of electronic devices, further thinning of the printed wiring board is progressing. As a result, miniaturization of the wiring circuit in the innerlayer substrate is progressing. For example, Patent Document 1 describes a resin sheet (adhesive film) capable of coping with fine wiring, including a support and a resin composition layer.

Japanese Patent Application Laid-Open No. 2014-36051

The inventors of the present invention studied thinning of the resin composition layer of the resin sheet in order to achieve further miniaturization and thinning of electronic equipment. As a result of the study, the present inventors have found that when a thin resin composition layer is applied to an insulating layer, a haloing phenomenon occurs after the formation of the via hole. Here, the haloing phenomenon refers to a phenomenon in which the resin of the insulating layer is discolored around the via-hole. Such a haloing phenomenon is usually caused by deterioration of the resin around the via-hole. In addition, when the roughening treatment is performed on the insulating layer in which the haloing phenomenon has occurred, the resin of the portion of the insulating layer in which the haloing phenomenon has occurred (hereinafter also referred to as the "halo portion") is eroded during the roughening treatment, It was found that interlayer delamination occurred with the inner layer substrate.

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

All of the above problems have arisen only when the thickness of the resin composition layer is made thin, which is a new problem which has not been known in the past. From the viewpoint of enhancing the conduction reliability between the layers of the printed wiring board, such a problem is desired to be solved.

SUMMARY OF THE INVENTION The present invention has been devised in view of the above problems, and it is an object of the present invention to provide a resin composition layer capable of suppressing a haloing phenomenon even if the thickness is thin, and capable of forming an insulating layer capable of forming a via- A resin sheet containing the above-mentioned resin composition layer; A printed wiring board including a thin insulating layer capable of suppressing a haloing phenomenon and capable of forming a via-hole of a good shape; And a semiconductor device including the above printed wiring board.

(B) an aromatic hydrocarbon resin containing an aromatic ring as a monocyclic or condensed ring having two or more hydroxyl groups, and (C) 100 And an inorganic filler having at least one of an average particle diameter of 10 nm or less and a specific surface area of 15 m 2 / g or more.

That is, the present invention includes the following contents.

[1] A resin composition layer having a thickness of 15 탆 or less including the resin composition,

Wherein the resin composition comprises (A) an epoxy resin, (B) an aromatic hydrocarbon resin containing an aromatic ring as a monocyclic or condensed ring having two or more hydroxyl groups, and (C) an inorganic filler having an average particle diameter of 100 nm or less. Resin composition layer.

[2] As the resin composition layer having a thickness of 15 탆 or less including the resin composition,

Wherein the resin composition comprises (A) an epoxy resin, (B) an aromatic hydrocarbon resin containing an aromatic ring as a monocyclic or condensed ring having two or more hydroxyl groups, and (C) an inorganic filler having a specific surface area of 15 m2 / Resin composition layer.

[3] The resin composition layer according to [1] or [2], wherein the component (B) is represented by the following formula (1) or (2).

[Chemical Formula 1]

(In the general formula (1), R ⁰ independently represents a divalent hydrocarbon group, and n1 represents an integer of 0 to 6)

(2)

(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 component (B) is represented by the following general formula (3) or (4)

(3)

(In the general formula (3), n2 represents an integer of 0 to 6)

[Chemical Formula 4]

(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 with respect to 100% by mass of the resin component in the resin composition.

[6] The resin composition layer according to any one of [1] to [5], 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.

[7] The resin composition layer according to any one of [1] to [6], which is for forming an insulating layer for forming a conductor layer.

[8] A resin composition layer according to any one of [1] to [7], which is for forming an interlayer insulating layer of a printed wiring board.

[9] The resin composition layer according to any one of [1] to [8], wherein the resin composition layer is for forming an insulating layer having a via-hole with a top diameter of 35 μm or less.

[10]

A resin sheet comprising the resin composition layer according to any one of [1] to [9] formed on a 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 an insulating layer formed between the first conductor layer and the second conductor layer,

The thickness of the insulating layer is 15 占 퐉 or less,

Wherein the insulating layer has a via hole with a top diameter of 35 mu m or less,

The taper ratio of the via hole is 80% or more,

The haloing distance from the edge of the bottom of the via hole is 5 占 퐉 or less,

And the haloing ratio to the bottom radius of the via-hole is 35% or less.

[13] The printed wiring board according to [12], wherein the haloing ratio to the bottom radius of the via-hole is 5% or more.

[14] A semiconductor device comprising the printed wiring board according to any one of [11] to [13].

According to the present invention, it is possible to provide a resin composition layer capable of suppressing a haloing phenomenon even when the thickness is thin, and capable of forming an insulating layer capable of forming a via-hole of a good shape; A resin sheet containing the above-mentioned resin composition layer; A printed wiring board including a thin insulating layer capable of suppressing a haloing phenomenon and capable of forming a via-hole of a good shape; And a semiconductor device including the above printed wiring board.

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

Hereinafter, embodiments and examples are shown, and the present invention will be described in detail. It should be noted, however, that the present invention is not limited to the following embodiments and examples, and can be arbitrarily changed without departing from the scope of the claims of the present invention and its equivalent scope.

In the following description, the "resin component" of the resin composition means a component other than the inorganic filler among the nonvolatile components contained in the resin composition.

[One. Resin Composition Layer Outline]

The resin composition layer of the present invention is a layer of a thin resin composition having a thickness of a predetermined value or less. In addition, the resin composition comprising the resin composition layer of the present invention,

(A) an epoxy resin,

(B) an aromatic hydrocarbon resin containing an aromatic ring as a monocyclic or condensed ring having two or more hydroxyl groups, and

(C) 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.

Therefore, the resin composition contained in the resin composition layer of the present invention may include any of the following first resin composition and second resin composition.

(A) an epoxy resin, (B) an aromatic hydrocarbon resin containing an aromatic ring as a monocyclic or condensed ring having two or more hydroxyl groups, and (C) an inorganic filler having an average particle diameter of 100 nm or less .

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

By using such a resin composition layer, a thin insulating layer can be obtained. In addition, a desired effect of the present invention can be obtained in that a via-hole having a good shape can be formed on the obtained insulating layer while suppressing the haloing phenomenon.

[2. (A): epoxy resin]

Examples of the epoxy resin as the component (A) include epoxy resins such as a bicyclanol type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a bisphenol AF type epoxy resin, a dicyclopentadiene type epoxy resin , Trisphenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidyl amine type Epoxy resins, glycidyl ester type epoxy resins, cresol novolak type epoxy resins, biphenyl type epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, A resin, a cyclohexane type epoxy resin, a cyclohexane dimethanol type epoxy resin, a naphthylene ether There may be mentioned epoxy resins, trimethyl olhyeong epoxy resin, tetraphenyl ethane epoxy resin and the like. The epoxy resin may be used alone, or two or more epoxy resins may be used in combination.

The resin composition preferably contains, as the epoxy resin (A), an epoxy resin having two or more epoxy groups in one molecule. From the viewpoint of obtaining the desired effect of the present invention remarkably, the ratio of the epoxy resin having two or more epoxy groups in one molecule to (A) 100% by mass of the nonvolatile component of the epoxy resin is preferably 50% by mass or more, More preferably not less than 60% by mass, particularly preferably not less than 70% by mass.

The epoxy resin includes epoxy resin (hereinafter sometimes referred to as " liquid epoxy resin ") which is liquid at a temperature of 20 캜, epoxy resin which is solid at a temperature of 20 캜 (hereinafter sometimes referred to as " solid epoxy resin " . The resin composition may contain only (A) the liquid epoxy resin as the epoxy resin, and may contain only the solid epoxy resin, but it is preferable to include the liquid epoxy resin and the solid epoxy resin in combination. (A) By using a combination of a liquid epoxy resin and a solid epoxy resin as the epoxy resin, it is possible to improve the flexibility of the resin composition layer or to improve the fracture strength of the cured product of the resin composition layer.

As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferable, and an aromatic liquid epoxy resin having two or more epoxy groups in one molecule is more preferable. Here, the "aromatic-based" epoxy resin means an epoxy resin having an aromatic ring in its molecule.

Examples of the liquid epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolak type epoxy resin , An alicyclic epoxy resin having an ester skeleton, a cyclohexane-type epoxy resin, a cyclohexane dimethanol-type epoxy resin, a glycidylamine-type epoxy resin, and an epoxy resin having a butadiene structure are preferable. Bisphenol A type epoxy resins, F type epoxy resin and cyclohexane type epoxy resin are more preferable.

Specific examples of the liquid epoxy resin include " HP4032 ", " HP4032D ", " HP4032SS " (naphthalene type epoxy resin) manufactured by DIC Corporation; "828US", "jER828EL", "825", "Epikote 828EL" (bisphenol A type epoxy resin) manufactured by Mitsubishi Kagaku; &Quot; jER807 ", " 1750 " (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation; &Quot; jER152 " (phenol novolak type epoxy resin) manufactured by Mitsubishi Chemical Corporation; 630 ", " 630LSD " (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; ZX1059 " (a mixture of a bisphenol A type epoxy resin and a bisphenol F type epoxy resin) manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd.; EX-721 " (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Corporation; &Quot; Verticalkide 2021P " (an alicyclic epoxy resin having an ester skeleton) manufactured by DICEL Corporation; &Quot; PB-3600 " (epoxy resin having a butadiene structure) manufactured by Daicel Company; ZX1658 " and " ZX1658GS " (liquid 1,4-glycidyl cyclohexane type epoxy resin) manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., and the like. These may be used singly or in combination of two or more.

As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferable, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferable.

Examples of the solid epoxy resin include epoxy resins such as bicalcylenol type epoxy resins, naphthalene type epoxy resins, naphthalene type tetrafunctional epoxy resins, cresol novolak type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol type epoxy resins, Epoxy resins such as phenylene type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin and tetraphenyl ethane type epoxy resin are preferable, and biscylenol type epoxy resin, Bisphenol AF type epoxy resin, and naphthylene ether type epoxy resin are more preferable.

Specific examples of the solid epoxy resin include " HP4032H " (naphthalene type epoxy resin) manufactured by DIC Corporation; HP-4700 ", " HP-4710 " (naphthalene type tetrafunctional epoxy resin) manufactured by DIC Corporation; "N-690" (cresol novolak type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolak type epoxy resin) manufactured by DIC Corporation; HP-7200 " (dicyclopentadiene type epoxy resin) manufactured by DIC Corporation; EXA-7311-G4 "," EXA-7311-G4S ", and" HP6000 "(manufactured by DIC Corporation," HP-7200HH "," HP-7200H "," EXA-7311 " Naphthylene ether type epoxy resin); "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; NC7000L " (naphthol novolak type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; Quot; NC3000H ", " NC3000 ", " NC3000L ", and " NC3100 " (biphenyl type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "ESN475V" (naphthalene type epoxy resin) manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd.; "ESN485" (naphthol novolak type epoxy resin) manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd.; YX4000H ", " YX4000 ", and " YL6121 " manufactured by Mitsubishi Chemical Corporation (biphenyl type epoxy resin); &Quot; YX4000HK " (biquileneol type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd.; &Quot; YL7760 " (Bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation; &Quot; YL7800 " (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; &Quot; jER1010 " (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; And " jER1031S " (tetraphenyl ethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation. These may be used singly or in combination of two or more.

(A) When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, the ratio of these amounts (liquid epoxy resin: solid epoxy resin) is preferably 1: 1 to 1:20, more preferably 1: 2 to 1:15, particularly preferably 1: 5 to 1:13. When the ratio of the liquid epoxy resin to the solid epoxy resin is in this range, the desired effect of the present invention can be obtained remarkably. Usually, when used in the form of a resin sheet, appropriate tackiness is caused. In general, when used in the form of a resin sheet, sufficient flexibility is obtained and handling properties are improved. Usually, a cured product having sufficient breaking strength can be obtained.

The epoxy equivalent of the epoxy resin (A) is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, still more preferably 110 to 1000. With such a range, the cross-linking density of the cured product of the resin composition layer becomes sufficient, and an insulating layer having a small surface roughness may be caused. The epoxy equivalent is the mass of the resin containing one equivalent of epoxy group. Such an epoxy equivalent can be measured according to JIS K7236.

The weight average molecular weight (Mw) of the epoxy resin (A) is preferably 100 to 5000, more preferably 250 to 3000, and still more preferably 400 to 1500, from the viewpoint of obtaining the desired effect of the present invention.

The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by a gel permeation chromatography (GPC) method.

The amount of the epoxy resin (A) in the resin composition is preferably 10% by mass or more, more preferably 10% by mass or more, and most preferably 10% by mass or more, based on 100% by mass of the resin component in the resin composition, from the viewpoint of obtaining an insulating layer showing good mechanical strength and insulation reliability 20 mass% or more, and more preferably 30 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 achieving the desired effect of the present invention.

[3. (B): aromatic hydrocarbon resin containing an aromatic ring as a monocyclic or condensed ring having two or more hydroxyl groups]

The resin composition includes, as the component (B), an aromatic hydrocarbon resin containing an aromatic ring having two or more hydroxyl groups. Normally, the component (B) can react with the epoxy resin (A) by the hydroxyl group of the aromatic ring, and therefore the component (B) can function as a curing agent for curing the resin composition. The haloing phenomenon can be suppressed by the action of the component (B).

Here, the term " aromatic ring " includes an aromatic ring as a monocyclic ring such as a benzene ring and an aromatic ring as 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, preferably 14 or less, more preferably 10 or less, more preferably 10 or less, from the viewpoint of obtaining a desired effect of the present invention remarkably. Or less.

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

At least one of the aromatic rings contained in the aromatic hydrocarbon resin as the component (B) has at least two hydroxyl groups per aromatic ring. The number of hydroxyl groups per aromatic ring is preferably 3 or less and particularly preferably 2 from the viewpoint of obtaining a desired effect of the present invention remarkably.

The number of aromatic rings having two or more hydroxyl groups per molecule of the component (B) is usually one or more, and preferably 2 or more, and more preferably 3 Or more. The upper limit is not particularly limited, but is preferably 6 or less, and more preferably 5 or less, from the viewpoint of suppressing steric hindrance and enhancing reactivity with the epoxy resin.

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).

[Chemical Formula 1]

(2)

In the general formula (1), R ⁰ represents, independently of each other, a divalent hydrocarbon group. The divalent hydrocarbon group may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The number of carbon atoms of the divalent hydrocarbon group is usually 1 or more and can be preferably 3 or more, 6 or more, or 7 or more from the viewpoint of obtaining the desired effect of the present invention remarkably. 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 achieving the desired effect of the present invention.

Specific examples of R ⁰ include the following hydrocarbon groups.

In the general 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, preferably 4 or less, more preferably 3 or less, from the viewpoint of obtaining a desired effect of the present invention remarkably.

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

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

Among them, particularly preferable aromatic hydrocarbon resins as the component (B) include an aromatic hydrocarbon resin represented by the following formula (3) and an aromatic hydrocarbon resin represented by the following formula (4). In the general formula (3), n2 represents an integer defined in the same manner as n1 in the general formula (1), and the preferable range is also the same. Also, it is the same as R ¹ to R ⁴ in the formula (2) in the general formula 4, R ¹ to R ^4.

(3)

[Chemical Formula 4]

As a commercial product of the aromatic hydrocarbon resin represented by the formula (3), for example, a naphthol-based curing agent "SN395" manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., represented by the following formula (5) In formula (5), n3 represents 2 or 3. As a commercially available product of the aromatic hydrocarbon resin represented by the general formula (4), for example, a phenol-based curing agent "GRA13H" manufactured by Aikagaku Kogyo Co., Ltd. may be mentioned.

[Chemical Formula 5]

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

The hydroxyl group equivalent of the component (B) is preferably not less than 50 g / eq, more preferably not less than 50 g / eq, from the viewpoint of increasing the crosslinking density of the insulating layer as the cured product of the resin composition layer and obtaining the desired effect of the present invention remarkably Eq or more, more preferably 70 g / eq or more, further preferably 200 g / eq or less, more preferably 150 g / eq or less, particularly preferably 120 g / eq or less. The hydroxyl equivalent is the mass of the resin containing one equivalent of hydroxyl groups.

The amount of the component (B) in the resin composition is preferably 5% by mass or more, more preferably 7% by mass or more, particularly preferably 9% by mass or more, relative to 100% by mass of the resin component in the resin composition, Is not more than 50 mass%, more preferably not more than 40 mass%, not more than 30 mass%, or not more than 20 mass%. When the amount of the component (B) is in the above range, the haloing phenomenon can be effectively suppressed.

(B) is preferably 5 mass% or more, more preferably 8 mass% or more, particularly preferably 10 mass% or more, and preferably 100 mass% or more, relative to 100 mass% of the epoxy resin (A) Or less, more preferably 50 mass% or less, and particularly preferably 30 mass% or less. When the amount of the component (B) is in the above range, the haloing phenomenon can be effectively suppressed.

When the number of epoxy groups in the epoxy resin (A) is 1, the number of hydroxyl groups in the component (B) is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.3 or more, More preferably 1.5 or less, further preferably 1 or less, particularly preferably 0.5 or less. Here, the "epoxy group number of the epoxy resin (A)" is a value obtained by dividing the mass of the nonvolatile component of the component (A) present in the resin composition by the epoxy equivalent. The "hydroxyl number of the component (B)" is a value obtained by dividing the mass of the nonvolatile component of the component (B) present in the resin composition by the hydroxyl equivalent. When the number of hydroxyl groups in the component (B) in the case where the number of epoxy groups in the epoxy resin (A) is 1, the haloing phenomenon can be effectively suppressed.

[4. (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]

The resin composition includes, as the component (C), an inorganic filler. 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 reflow warpage is suppressed can be obtained. 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. As the inorganic filler, by using the component (C) having at least one of the average particle diameter and the specific surface area in such a range in combination with the component (B), it is possible to realize an insulating layer capable of forming a via hole having a good shape.

As a material of the inorganic filler, an inorganic compound is used. Examples of the material of the inorganic filler include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, Calcium carbonate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium titanate zirconate, zirconium titanate, zirconium titanate, zirconium oxide, zirconium oxide, Barium oxide, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Of these, silica is particularly suitable. As the silica, for example, amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica and the like can be given. As the silica, spherical silica is preferable. The inorganic fillers may be used singly or in combination of two or more kinds.

The average particle diameter of the component (C) is usually 100 nm or less, preferably 90 nm or less, more preferably 90 nm or less, from the viewpoint of thinning the insulating layer and from the viewpoint of realizing a good shape, Is 80 nm or less. 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. Examples of commercially available inorganic fillers having such an average particle diameter include "UFP-30" and "UFP-40" manufactured by Denki Kagaku Koh Corporation.

The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, the particle diameter distribution of the inorganic filler can be measured with a laser diffraction scattering type particle diameter distribution measuring apparatus, and the average particle diameter can be measured by forming the particle diameter based on volume. As the measurement sample, an inorganic filler dispersed in methyl ethyl ketone by ultrasonic waves can be preferably used. As the laser diffraction scattering type particle diameter distribution measuring apparatus, "LA-500" manufactured by Horiba Seisakusho Co., Ltd., "SALD-2200" manufactured by Shimadzu Corporation can be used.

The specific surface area of the component (C) is usually at least 15 m 2 / g, preferably at least 20 m 2 / g, particularly preferably at least 30 m 2 / g, from the viewpoint of facilitating the control of via- Or more. In addition, the component (C) having a large specific surface area as described above generally has a small particle diameter, so that 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 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. As the surface treatment agent, for example, a fluorine-containing silane coupling agent, an aminosilane coupling agent, an epoxy silane coupling agent, a mercaptosilane coupling agent, a silane coupling agent, an alkoxysilane, an organosilazane compound, LINGER, and the like. The surface treatment agent may be used singly or in combination of two or more kinds.

Examples of commercially available products of the surface treatment agent include KBM403 (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., KBM803 (3-mercaptopropyltrimethoxy Silane), KBE903 (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., KBM573 (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin- KBM103 "(phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.," KBM-4803 "manufactured by Shin-Etsu Chemical Co., Ltd. (long-chain epoxy-type silane couples , KBM-7103 (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

The degree of surface treatment by the surface treatment agent is preferably within a predetermined range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, 100 parts by mass of the inorganic filler is preferably surface-treated with 0.2 to 5 parts by mass of the surface treating agent, preferably 0.2 to 3 parts by mass, more preferably 0.3 to 2 parts by mass It is preferable that it is surface-treated.

The degree of the 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 at least 0.02 mg / m 2, more preferably at least 0.1 mg / m 2, and most preferably at least 0.2 mg / m 2 from the viewpoint of improving the dispersibility of the inorganic filler. On the other hand, from the viewpoint of suppressing the increase of the melt viscosity and the melt viscosity in the sheet form of the resin varnish, it is preferably 1 mg / m 2 or less, more preferably 0.8 mg / m 2 or less, and further preferably 0.5 mg / .

The amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with the surface treatment agent, and ultrasonically cleaned at 25 占 폚 for 5 minutes. After the supernatant is removed and the solid content is dried, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by Horiba Seisakusho Co., Ltd. and the like can be used.

The amount of the component (C) in the resin composition is preferably not less than 30% by mass, more preferably not less than 35% by mass, 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 , And more preferably 40 mass% or more. In addition, when the layer of the resin composition containing such an inorganic filler is thin, it is difficult to improve the shape of the via hole. In particular, when the amount of the inorganic filler relative to 100% by mass of the nonvolatile component in the resin composition is 50 If it is more than% by mass, formation of a via hole having a good shape is particularly difficult. Therefore, from the viewpoint of effectively utilizing the advantage of the present invention that a via hole of a good shape which is conventionally difficult to form in the past, the amount of the component (C) relative to 100 mass% of the nonvolatile component in the resin composition is preferably 50 By mass or more, more preferably 54% by mass or more. The upper limit of the amount of the component (C) relative to 100 mass% of the nonvolatile component in the resin composition is preferably 90 mass% or less, more preferably 85 mass% or less, still more preferably 85 mass% Is 80 mass% or less, or 75 mass% or less.

[5. (D) Component: 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 thermoplastic resins such as phenoxy resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyimide resins, polyamideimide resins, polyetherimide resins, polysulfone resins, Resins, polyphenylene ether resins, polycarbonate resins, polyether ether ketone resins, and polyester resins. Among them, a phenoxy resin is preferable from the viewpoint of obtaining a desired effect of the present invention remarkably and from the viewpoint of obtaining an insulating layer particularly excellent in adhesion to a conductor layer having a small surface roughness. The thermoplastic resin may be used singly or in combination of two or more kinds.

Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolak skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, A phenoxy resin having at least one skeleton selected from the group consisting of a skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethyl cyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group.

Specific examples of the phenoxy resin include " 1256 " and " 4250 " (all phenolic resin containing bisphenol A skeleton) manufactured by Mitsubishi Chemical Corporation; &Quot; YX8100 " (bisphenol S skeleton-containing phenoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX6954" (a phenoxy resin containing a bisphenol acetophenone skeleton) manufactured by Mitsubishi Chemical Corporation; &Quot; FX280 " and " FX293 " manufactured by Shinnitetsu Sumikin Kagaku; YL7500BH30, YX6954BH30, YX7553, YX7553BH30, YL7769BH30, YL6794, YL7213, YL7290 and YL7482 manufactured by Mitsubishi Kagaku Co.,

As the polyvinyl acetal resin, for example, a polyvinyl formal resin and a polyvinyl butyral resin can be mentioned, and a polyvinyl butyral resin is preferable. Specific examples of the polyvinyl acetal resin include "Denkabutilal 4000-2", "Denkabutilal 5000-A", "Denkabutilal 6000-C", "Denkabutilal 6000-EP" manufactured by Denki Kagaku Kogyo Co., ; (For example, BX-5Z), KS series (for example, KS-1), BL series, and BM series manufactured by Sekisui Kagaku Kogyo Co., Ltd.

Specific examples of the polyimide resin include "Rika coat SN20" and "Rika coat PN20" manufactured by Shin-Nihon Rika Co., Ltd. Specific examples of the polyimide resin include a linear polyimide (polyimide disclosed in JP-A 2006-37083) obtained by reacting a bifunctional hydroxyl-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride, Modified polyimides such as polysiloxane skeleton-containing polyimide (Japanese Patent Application Laid-Open No. 2002-12667 and Japanese Patent Application Laid-Open No. 2000-319386, etc.).

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

Specific examples of the polyether sulfone resin include "PES 5003P" manufactured by Sumitomo Chemical Co., Ltd.

Specific examples of the polyphenylene ether resin include an oligophenylene ether styrene resin "OPE-2St 1200" manufactured by Mitsubishi Gas Kagaku Co., Ltd. and the like.

Specific examples of the polysulfone resin include polysulfone "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, from the viewpoint of obtaining the desired effect of the present invention remarkably, Preferably 70,000 or less, more preferably 60,000 or less, particularly preferably 50,000 or less.

When the thermoplastic resin (D) is used, the amount of the thermoplastic resin (D) in the resin composition is preferably from 0.1 mass% to 100 mass% of the resin component in the resin composition from the viewpoint of achieving the desired effect of the present invention More preferably not less than 0.5% by mass, more preferably not less than 1% by mass, preferably not more than 15% by mass, more preferably not more than 12% by mass, further preferably not more than 10% by mass.

[6. Component (E): 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 curing agent as the component (E), those having a function of curing the component (A) can be used. Examples of the (E) curing agent include an active ester type curing agent, a phenol type curing agent, a naphthol type curing agent, a benzoxazine type curing agent, a cyanate ester type curing agent and a carbodiimide type curing agent. The curing agent may be used singly or in combination of two or more kinds. Among them, an active ester-based curing agent is preferable in view of obtaining a desired effect of the present invention remarkably.

As the active ester type curing agent, a compound having at least one active ester group in one molecule can be used. Among them, examples of the active ester curing agent include esters having two or more ester groups having high reactivity, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds Compounds are preferred. It is preferable that the active ester curing agent is 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. Particularly, from the viewpoint of improving the heat resistance, active ester curing agents obtained from carboxylic acid compounds and hydroxy compounds are preferable, and active ester curing agents obtained from carboxylic acid compounds and phenol compounds and / or naphthol compounds are more preferable .

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

Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o- Cresol, catechol, alpha -naphthol, beta -naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, Trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglucine, benzene triol, dicyclopentadiene type diphenol compounds, phenol novolak, and the like. Here, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol in one dicyclopentadiene molecule.

Specific preferred examples of the active ester-based curing agent include active ester compounds containing a dicyclopentadiene type diphenol structure, active ester compounds containing a naphthalene structure, active ester compounds containing an acetylated phenol novolac, And an active ester compound including a benzoylate. Of these, active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene type diphenol structure are more preferable. The "dicyclopentadiene-type diphenol structure" refers to a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

EXB9451 "," EXB9460 "," EXB9460S "," HPC-8000-65T "," HPC-8000H-65TM ", and the like are available as commercial products of the active ester- EXB-8000L-65TM ", " EXB-8150-65T " (manufactured by DIC Corporation); EXB9416-70BK " (manufactured by DIC) as an active ester compound containing a naphthalene structure; &Quot; DC808 " (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing an acetylated phenol novolak; &Quot; YLH1026 " (manufactured by Mitsubishi Kagaku Co., Ltd.) as the active ester compound containing benzoylated phenol novolak; DC808 " (manufactured by Mitsubishi Kagaku Co., Ltd.) as an active ester-based curing agent which is an acetylated product of phenol novolak; YLH1026 " (manufactured by Mitsubishi Kagaku), " YLH1030 " (manufactured by Mitsubishi Kagaku), and " YLH1048 " (manufactured by Mitsubishi Kagaku Co., Ltd.) as the benzoylates of phenol novolak.

As the phenol-based curing agent and naphthol-based curing agent, those having a novolak structure are preferable from the viewpoints of heat resistance and water resistance. Further, from the viewpoint of adhesion with a conductor layer, a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent is more preferable.

Specific examples of the phenol-based curing agent and naphthol-based curing agent include "MEH-7700", "MEH-7810" and "MEH-7851" manufactured by Meiwa Kasei; NHN ", " CBN ", " GPH ", manufactured by Nippon Kayaku Co., "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V" and "SN375" manufactured by Shinnetsu Tetsu Sumikin Kagaku Co., TD-2090 "," LA-7052 "," LA-7054 "," LA-1356 "," LA-3018-50P "and" EXB-9500 "manufactured by DIC Corporation.

Specific examples of the benzoxazine-based curing agent include "HFB2006M" manufactured by Showa Kogane Co., Ltd., "P-d" and "F-a" manufactured by Shikoku Kasei Corporation.

Examples of the cyanate ester curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4'- Dimethylphenyl cyanate), 4,4'-ethylidenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1- Cyanate phenylmethane), bis (4-cyanate-3,5-dimethylphenyl) methane, 1,3-bis Naphthyl phenyl) thioether, and bis (4-cyanate phenyl) ether; Polyfunctional cyanate resins derived from phenol novolak and cresol novolak; And a partially triarylated prepolymer of these cyanate resins. Specific examples of the cyanate ester curing agent include "PT30" and "PT60" (phenol novolac type polyfunctional cyanate ester resin), "ULL-950S" (multifunctional cyanate ester resin), "BA230 , And " BA230S75 " (a prepolymer obtained by trimerizing a part or all of bisphenol A dicyanate and becoming a trimer).

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

When the (E) curing agent is used, the amount of the (E) curing agent in the resin composition is preferably at least 0.1% by mass or more, more preferably at least 0.1% by mass with respect to 100% by mass of the resin component in the resin composition, , More preferably not less than 0.5 mass%, further preferably not less than 1 mass%, preferably not more than 20 mass%, more preferably not more than 15 mass%, further preferably not more than 12 mass%.

When the (E) curing agent is used, the amount of the (E) curing agent in the resin composition is preferably 40 mass% or more, more preferably 40 mass% or less, , More preferably not less than 50 mass%, particularly preferably not less than 60 mass%, preferably not more than 120 mass%, more preferably not more than 100 mass%, particularly preferably not more than 90 mass%.

When the number of epoxy groups in the epoxy resin (A) is 1, the number of active groups in the component (E) is preferably 0.1 or more, more preferably 0.2 or more, and preferably 2 or less, 1.5 or less, more preferably 1 or less, particularly preferably 0.5 or less. Here, the "number of active groups of the component (E)" is a value obtained by summing the values obtained by dividing the mass of the non-volatile component of the component (E) present in the resin composition by the active group equivalent. When the number of active groups of the component (E) in the case where the number of epoxy groups in the epoxy resin (A) is 1, the insulating layer having particularly excellent mechanical strength can be obtained.

[7. (F): Curing accelerator]

The resin composition may further contain, as optional components, (C) a curing accelerator in addition to the above components.

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

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

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

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl- Benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl- 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium Trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] -ethyl-s-triazine, 2,4- diamino-6- [ Imidazolyl- (1 ')] - ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- Triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] - ethyl- , 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3- Dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline and 2-phenylimidazoline An imidazole compound and an adduct of an imidazole compound and an epoxy resin, and 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferable.

As the imidazole-based curing accelerator, a commercially available product may be used, and for example, " P200-H50 " manufactured by Mitsubishi Kagaku Co.,

Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, , Trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] deca-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1- (o-tolyl) biguanide, and the like, and dicyandiamide, 1,5,7-triazabicyclo [4.4.0] deca-5-ene are preferred.

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

When the (F) curing accelerator is used, the amount of the (C) curing accelerator in the resin composition is preferably 0.01 mass% More preferably not less than 0.05% by mass, more preferably not less than 0.1% by mass, preferably not more than 3% by mass, more preferably not more than 2% by mass, further preferably not more than 1.5% by mass.

[8. (G) component: optional additive]

The resin composition may further contain optional additives as optional components in addition to the above components. Such additives include, for example, organic fillers; Organic metal compounds such as organic copper compounds, organic zinc compounds and organic cobalt compounds; A flame retardant, a thickener, a defoaming agent, a leveling agent, an adhesion promoter, and a colorant. These additives may be used singly or in combination of two or more kinds.

[9. Thickness of resin composition layer]

The resin composition layer is a layer formed of the resin composition described above and has a thickness of a predetermined value or less. The specific thickness of the resin composition layer is usually 15 占 퐉 or less, preferably 14 占 퐉 or less, more preferably 12 占 퐉 or less. Conventionally, the thickness of the resin composition layer for forming the insulating layer of the printed wiring board is generally thicker than that. On the other hand, the present inventors found that such a thin resin composition layer as described above has a problem in that the generation of the haloing phenomenon and the difficulty in controlling the shape of the via-hole become difficult, found. From the viewpoint of solving these new problems and contributing to the thinning of the printed wiring board, the resin composition layer of the present invention is formed as described above. The lower limit of the thickness of the resin composition layer is arbitrary, and may be, for example, 1 占 퐉 or more and 3 占 퐉 or more.

[10. Properties 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 via-hole having a good shape can be formed. Further, when a via hole is formed in such an insulating layer, the haloing phenomenon can be suppressed. Hereinafter, such effects will be described with reference to the drawings.

Fig. 1 is a cross-sectional view schematically showing an insulating layer 100 obtained by curing a resin composition layer according to the first embodiment of the present invention together with an inner layer substrate 200. Fig. 1 shows a cross section in which the insulating layer 100 is cut in a plane that passes through the center 120C of the bottom 120 of the via hole 110 and is 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 an inner layer substrate 200 including a conductor layer 210, And a cured product of the resin composition layer. In the insulating layer 100, a via hole 110 is formed. The diameter of the via hole 110 is larger toward the surface 100U of the insulating layer 100 on the opposite side to the conductor layer 210 and the diameter of the via hole 110 is smaller toward the conductor layer 210 And is ideally formed into a columnar shape having a certain diameter in the thickness direction of the insulating layer 100. [ The via hole 110 is formed by irradiating the surface 100U of the insulating layer 100 on the opposite side of the conductive layer 210 with a laser beam to remove a part of the insulating layer 100. [

The bottom of the via hole 110 on the side of the conductor layer 210 is referred to as a "via bottom", and is denoted by reference numeral 120. The diameter of the via bottom 120 is referred to as a bottom diameter Lb. The openings formed on the side of the via hole 110 opposite to the conductor layer 210 are referred to as " via-tops " The diameter of the via-top 130 is referred to as a top diameter Lt. Typically, the via-bottom 120 and the via-top 130 are formed in a circular shape in plan view as viewed from the thickness direction of the insulating layer 100, but may be elliptical. When the planar shape of the via bottom 120 and the via top 130 is elliptical, the bottom diameter Lb and the tower diameter Lt respectively represent the long diameter of the elliptical shape described above.

At this time, as the taper ratio Lb / LT (%) obtained by dividing the bottom diameter Lb by the top diameter Lt is closer to 100%, the shape of the via hole 110 is favorable. When the resin composition layer of the present invention is used, since the shape of the via hole 110 can be easily controlled, the via 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 占 폚 for 30 minutes and then heating at 180 占 폚 for 30 minutes to cure was coated with a resist film having a mask diameter of 1 mm, a pulse width of 16 占 퐏, an energy of 0.2 mJ / Hole 110 having a top diameter Lt of 30 mu m +/- 2 mu m is formed by irradiating CO ₂ laser light under the conditions of the number of shots 2, the burst mode (10 kHz) Preferably 60% to 100%, more preferably 70% to 100%, and particularly preferably 80% to 100%, of the taper ratio Lb /

The taper ratio Lb / Lt of the via hole 110 can be calculated from the bottom diameter Lb of the via hole 110 and the top diameter Lt. The bottom diameter Lb and the columnar diameter Lt of the via hole 110 are set such that the insulating layer 100 is parallel to the thickness direction of the insulating layer 100 using a FIB (focused ion beam) The surface of the via bottom 120 is cut so that a section passing through the center 120C of the via bottom 120 appears, and the cross section is observed with an electron microscope.

2 shows the surface 100U on the opposite side of the conductor layer 210 (not shown in Fig. 2) of the insulating layer 100 obtained by curing the resin composition layer according to the first embodiment of the present invention, Fig.

2, when the insulating layer 100 in which the via hole 110 is formed is observed, the halo portion 140 in which the insulating layer 100 is discolored is observed around the via hole 110 have. Since the halo portion 140 can be formed by a haloing phenomenon at the time of forming the via hole 110, the halo portion 140 is formed continuously from the via hole 110. Further, in many cases, the halo portion 140 is a whitening portion.

By using the resin composition layer of the present invention, the haloing phenomenon described above can be suppressed. Therefore, the size of the halo portion 140 can be reduced, and ideally, the halo portion 140 can be eliminated. The size of the halo portion 140 can be evaluated by the haloing distance Wt from the edge 150 of the via hole 130 of the via hole 110. [

The edge 150 of the via top 130 corresponds to the edge portion on the inner circumferential side of the halo portion 140. The haloing distance Wt from the edge 150 of the via top 130 indicates the distance from the edge 150 of the via top 130 to the edge portion 160 on the outer circumferential side of the halo portion 140 . It can be estimated that the haloing phenomenon can be effectively suppressed as the haloing distance Wt from the edge 150 of the via top 130 is smaller.

For example, the insulating layer 100 obtained by heating the resin composition layer at 100 占 폚 for 30 minutes and then heating at 180 占 폚 for 30 minutes for curing has a mask 1 mm in diameter, a pulse width of 16 占 퐏, an energy of 0.2 mJ / When a via hole 110 having a top diameter Lt of 30 mu m +/- 2 mu m is formed by irradiating CO ₂ laser light under the conditions of the number of shots 2 and the burst mode (10 kHz), the edge of the via- The haloing distance Wt from the light emitting element 150 can be set to preferably 6 mu m or less, more preferably 5 mu m or less.

The haloing distance Wt from the edge 150 of the via top 130 can be measured by observation with an optical microscope.

Further, according to the study by the present inventors, it has been found that the size of the halo portion 140 tends to become larger as the diameter of the via hole 110 is larger. Therefore, the degree of suppression of the haloing phenomenon can be evaluated according to the ratio of the size of the halo portion 140 to the diameter of the via hole 110. Can be evaluated by, for example, the halo ingot Ht with respect to the top radius Lt / 2 of the via hole 110. Here, the top radius Lt / 2 of the via hole 110 refers to the radius of the via hole 130 of the via hole 110. The halo ingot Ht with respect to the top radius Lt / 2 of the via hole 110 is a distance from the edge 150 of the via top 130 to the haloing distance Wt of the via hole 110 Top radius (Lt / 2). The halo ingation phenomenon can be effectively suppressed as the halo ingot Ht with respect to the top radius (Lt / 2) of the via hole 110 becomes smaller.

For example, the insulating layer 100 obtained by heating the resin composition layer at 100 占 폚 for 30 minutes and then curing by heating at 180 占 폚 for 30 minutes was coated with a resist film having a mask diameter of 1 mm, a pulse width of 16 占 퐏, an energy of 0.2 mJ / Holes 110 having a top diameter Lt of 30 mu m +/- 2 mu m are formed by irradiating CO ₂ laser light under the conditions of the number of shots 2 and the burst mode (10 kHz) The halo ingot (Ht) with respect to the radius (Lt / 2) is preferably 45% or less, more preferably 40% or less, further preferably 35% or less.

The halo ingot Ht with respect to the top radius Lt / 2 of the via hole 110 is determined by the top diameter Lt of the via hole 110 and the edge 150 of the via hole 110 of the via hole 110 ) From the haloing distance (Wt)

Fig. 3 is a cross-sectional view schematically showing the roughened insulating layer 100 together with the inner layer substrate 200 obtained by curing the resin composition layer according to the first embodiment of the present invention. 3 shows a cross section in which the insulating layer 100 is cut in a plane that passes through the center 120C of the via bottom 120 of the via hole 110 and is parallel to the thickness direction of the insulating layer 100 .

3, the insulating layer 100 of the halo portion 140 is peeled off from the conductor layer 210 and the via-bottom (not shown) is removed by performing the roughening treatment on the insulating layer 100 having the via- 120 may be formed continuously from the edge 170 of the base member 120. The gap portion 180 is typically formed by eroding the halo portion 140 during the coarsening process.

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

The edge 170 of the via bottom 120 corresponds to the edge portion on the inner circumferential side of the gap portion 180. [ The distance from the edge 170 of the via bottom 120 to the end on the outer peripheral side of the gap portion 180 (i.e., the end on the side far from the center 120C of the via bottom 120) Wb correspond to the size of the gap portion 180 in the in-plane direction. Here, the in-plane direction refers to a direction perpendicular to the thickness direction of the insulating layer 100. In the following description, the distance Wb may be referred to as the haloing distance Wb from the edge 170 of the via bottom 120 of the via hole 110.

The suppressing degree of the formation of the gap portion 180 can be evaluated by the haloing distance Wb from the edge 170 of the via bottom 120. [ Concretely, it can be estimated that the smaller the haloing distance Wb from the edge 170 of the via bottom 120, the more effectively the formation of the gap portion 180 can be suppressed.

Since the gap portion 180 is formed by peeling off the insulating layer 100 of the halo portion 140, the size of the gap portion 180 is dependent on the size of the haloing phenomenon 140. Therefore, it can be estimated that the haloing phenomenon can be effectively suppressed as the haloing distance Wb from the edge 170 of the via bottom 120 becomes smaller.

For example, the insulating layer 100 obtained by heating the resin composition layer at 100 占 폚 for 30 minutes and then curing by heating at 180 占 폚 for 30 minutes was coated with a resist film having a mask diameter of 1 mm, a pulse width of 16 占 퐏, an energy of 0.2 mJ / The via hole 110 having a top diameter Lt of 30 mu m +/- 2 mu m is formed by irradiating CO ₂ laser light under the conditions of the number of shots 2 and the burst mode (10 kHz). Thereafter, the substrate is immersed in the swollen liquid at 60 DEG C for 10 minutes, then immersed in an oxidizing agent solution at 80 DEG C for 20 minutes, then immersed in a neutralized liquid at 40 DEG C for 5 minutes, and then dried at 80 DEG C for 15 minutes. When this harmonic treatment is performed, the haloing distance Wb from the edge 170 of the via bottom 120 is preferably 60 占 퐉 or less, more preferably 50 占 퐉 or less, particularly preferably 40 占 퐉 or less can do.

The haloing distance Wb from the edge 170 of the via bottom 120 can be adjusted by using a FIB (focused ion beam) to make the insulating layer 100 parallel to the thickness direction of the insulating layer 100, It can be measured by cutting out a section that passes through the center 120C of the bottom 120 and observing the section with an electron microscope.

According to the study by the inventor of the present invention, it is generally found that the larger the diameter of the via hole 110 is, the larger the size of the halo portion 140 is, and therefore, the size of the gap portion 180 tends to become larger have. Therefore, the degree of suppression of the haloing phenomenon can be evaluated according to the ratio of the size of the gap portion 180 to the diameter of the via hole 110, and furthermore, the degree of suppression of the formation of the gap portion 180 can be evaluated Can be evaluated. For example, it can be evaluated by the halo ingot Hb against the bottom radius Lb / 2 of the via hole 110. Here, the bottom radius Lb / 2 of the via hole 110 refers to the radius of the via bottom 120 of the via hole 110. The halo ingot Hb with respect to the bottom radius Lb / 2 of the via hole 110 is a distance from the edge 170 of the via bottom 120 to the halo distance Wb of the via hole 110 And the bottom radius (Lb / 2). The smaller the halo ratio Hb with respect to the bottom radius Lb / 2 of the via-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 占 폚 for 30 minutes and then curing by heating at 180 占 폚 for 30 minutes was coated with a resist film having a mask diameter of 1 mm, a pulse width of 16 占 퐏, an energy of 0.2 mJ / The via hole 110 having a top diameter Lt of 30 mu m +/- 2 mu m is formed by irradiating CO ₂ laser light under the conditions of the number of shots 2 and the burst mode (10 kHz). Subsequently, the substrate is immersed in a swollen liquid at 60 DEG C for 10 minutes, then immersed in an oxidizing agent solution at 80 DEG C for 20 minutes, then immersed in a neutralized liquid at 40 DEG C for 5 minutes, and then dried at 80 DEG C for 15 minutes. When such a harmonic treatment is performed, the halo ratio Hb to the bottom radius Lb / 2 of the via hole 110 is preferably 60% or less, more preferably 50% or less, further preferably 40% Or less.

The hole diameter Hb of the via hole 110 with respect to the bottom radius Lb / 2 is smaller than the bottom diameter Lb of the via hole 110 and the edge 170 of the via bottom 110 of the via hole 110 ) From the haloing distance (Wb)

The via hole 110 is formed in a state in which another conductor layer (not shown) is not provided on the surface 100U of the insulating layer 100 on the opposite side of the conductor layer 210 do. Therefore, when the manufacturing process of the printed wiring board is known, it is possible to clearly recognize the structure in which the via bottom 120 is present on the conductor layer 210 side and the via top 130 is opened on the side opposite to the conductor layer 210 have. However, there may be a case where the conductor layer is provided on both sides of the insulating layer 100 in the completed printed wiring board. In such a case, it may be difficult to distinguish the via bottom 120 from the via top 130 due to the positional relationship with the conductor layer. However, the top diameter Lt of the via-top 130 is generally equal to or larger than the bottom diameter Lb of the via bottom 120. Therefore, in the above case, it is possible to distinguish the via bottom 120 from the via top 130, depending on the diameter.

The inventors of the present invention presume a structure in which the above-mentioned effects can be obtained by the resin composition layer of the present invention as follows. However, the technical scope of the present invention is not limited by the structure described below.

Typically, when forming the via hole 110, energy such as heat and light is provided to the portion of the insulating layer 100 where the via hole 110 is to be formed. A part of the energy provided at this time may be transmitted around the portion where the via hole 110 is to be formed to cause the oxidation of the resin. When such oxidation occurs, the resin is deteriorated and may appear as a haloing phenomenon. However, since the component (B) has an aromatic ring having two or more hydroxyl groups, the progress of the oxidation reaction of the resin can be suppressed by the steric hindrance action of the hydroxyl group. Therefore, the haloing phenomenon can be suppressed in the insulating layer 100 obtained by using the resin composition layer of the present invention.

Further, as can be seen 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. The energy provided to the insulating layer 100 can be satisfactorily electrolyzed in the thickness direction of the insulating layer 100 since the particle diameter of the component (C) is small. For example, when thermal energy or light energy is provided to the surface 100U of the insulating layer 100, the energy can be transmitted in the thickness direction without generating large attenuation. Therefore, the via hole 110 having a large taper ratio can be easily formed, so that the shape of the via 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 purposes. Specifically, the resin composition layer of the present invention can be suitably used as a resin composition layer (a resin composition layer for forming an insulating layer of a printed wiring board) for forming an insulating layer of a printed wiring board, It can be more suitably used as a resin composition layer (resin composition layer for forming an interlayer insulating layer of a printed wiring board) for forming an insulating layer. The resin composition layer of the present invention may further comprise a resin composition layer for forming the insulating layer for forming a conductor layer (including a rewiring layer) on the insulating layer (a resin composition layer for forming an insulating layer ) Can be suitably used.

Particularly, from the viewpoint of effectively utilizing the advantage that the haloing phenomenon can be suppressed and the formation of the via-hole having a good shape can be effectively utilized, the above-mentioned resin composition layer is excellent in the resin composition for forming the insulating layer having via holes (A resin composition layer for forming an insulating layer having a via-hole), and is particularly suitable as a resin composition layer for forming an insulating layer having a via-hole with a column diameter of 35 m or less.

[12. Resin sheet]

The resin sheet of the present invention comprises a support and a resin composition layer of the present invention formed on the support.

As the support, for example, a film made of a plastic material, a metal foil and a release paper can be mentioned, and a film or a metal foil made of a plastic material is preferable.

When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter may be abbreviated as "PET"), polyethylene naphthalate (hereinafter abbreviated as "PEN" (Hereinafter sometimes abbreviated as "PC"), polymethyl methacrylate (hereinafter may be abbreviated as "PMMA"), and other polymers such as cyclic polyolefins, Triacetyl cellulose (hereinafter may be abbreviated as "TAC"), polyether sulfide (hereinafter sometimes abbreviated as "PES"), polyether ketone, polyimide and the like. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

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

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

As the support, a support having a release layer having a release layer on the surface to be bonded to the resin composition layer may be used. As the releasing agent for use in the release layer of the release layer-adhered support, for example, one or more release agents selected from the group consisting of an alkyd resin, a polyolefin resin, a urethane resin, and a silicone resin may be mentioned. SK-1, " " AL-5, " and " AL-5, " manufactured by LINTEX Corporation, each of which is a PET film having a releasing layer mainly composed of an alkyd resin-based releasing agent, 7 "; &Quot; Lumirra T60 " "Purex" manufactured by Teijin Co., Ltd.; And " UNIPHIL " manufactured by UniCasa.

The thickness of the support is not particularly limited, but is preferably in the range of 5 탆 to 75 탆, more preferably in the range of 10 탆 to 60 탆. When a release layer-adhered support is used, it is preferable that the thickness of the entirety of the release layer-adhered support is in the above range.

The resin sheet may contain any layer other than the support and the resin composition layer, if necessary. Examples of such arbitrary layers include a protective film based on a support formed on the surface of the resin composition layer not bonded to the support (i.e., the surface opposite to the support), and the like. The thickness of the protective film is not particularly limited, but is, for example, 1 m to 40 m. By the protective film, adhesion and scratches of dust or the like to the surface of the resin composition layer can be suppressed.

The resin sheet can be produced, for example, by preparing a resin varnish containing an organic solvent and a resin composition, coating the resin varnish on a support using a coating apparatus such as a die coater, and drying the resin varnish to form a resin composition layer can do.

Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone; Acetic acid ester solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate; Carbitol solvents such as cellosolve and butyl carbitol; Aromatic hydrocarbon solvents such as toluene and xylene; And amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. The organic solvent may be used singly or in combination of two or more kinds.

Drying may be carried out by heating, hot air blowing, or the like. The drying conditions are not particularly limited, but the drying is carried out so that the content of the organic solvent in the resin composition layer is usually 10 mass% or less, preferably 5 mass% or less. For example, 30% by mass to 60% by mass, is used, the resin varnish is dried at 50 ° C to 150 ° C for 3 minutes to 10 minutes to obtain a resin A composition layer can be formed.

The resin sheet can be rolled and stored. When the resin sheet has a protective film, it is usually usable by removing the protective film.

[13. Printed wiring board]

The printed wiring board of the present invention comprises an insulating layer formed of a cured product of the thin resin composition layer as described above. In addition, such an insulating layer can suppress the haloing phenomenon at the time of forming the via-hole, and can form a via-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 deterioration in performance due to deterioration of haloing phenomenon or via-hole shape.

The via-holes are usually formed to conduct the conductor layers formed on both sides of the insulating layer having the via-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. Then, a via hole is formed in the insulating layer, and the first conductor layer and the second conductor layer can be made conductive through the via hole.

By utilizing the advantage of the resin composition layer capable of suppressing the haloing phenomenon and forming a via-hole having 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 first conductor layer, a second conductor layer, and an insulating layer formed between the first conductor layer and the second conductor layer. The printed wiring board satisfies all of the following requirements (i) to (v) Satisfaction.

(i) the thickness of the insulating layer is 15 占 퐉 or less;

(ii) the insulating layer has a via hole with a top diameter of 35 mu m or less.

(iii) the taper ratio of the via hole is 80% or more.

(iv) the haloing distance from the edge of the via bottom of the via hole is 5 占 퐉 or less.

(v) the haloing ratio to the bottom radius of the via-hole is 35% or less.

Hereinafter, the specific printed wiring board will be described with reference to the drawings. 4 is a schematic cross-sectional view of a printed wiring board 300 according to a second embodiment of the present invention. 4 shows a cross section obtained by cutting the printed wiring board 300 in a plane passing through the center 120C of the via bottom 120 of the via hole 110 and parallel to the thickness direction of the insulating layer 100 . In Fig. 4, the parts corresponding to the elements described in Figs. 1 to 3 are denoted by the same reference numerals as those used in Figs. 1 to 3. Fig.

4, the specific printed wiring board 300 according to the second embodiment of the present invention includes a first conductor layer 210, a second conductor layer 220, a first conductor layer 210, 2 conductor layer 220. The insulating layer 100 may be formed of a conductive material. In the insulating layer 100, a via hole 110 is formed. In addition, the second conductor layer 220 is usually formed after the via hole 110 is formed. The second conductor layer 220 is formed not only in the surface 100U of the insulating layer 100 but also in the via hole 110 and is electrically connected to the first conductor layer 210 And the second conductor layer 220 are connected to each other.

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, particularly preferably 5 μm or less. Since the specific printed wiring board 300 has such a thin insulating layer 100, it is possible to achieve the thinning of the specific printed wiring board 300 itself. The lower limit of the thickness T of the insulating layer 100 is preferably 1 占 퐉 or more, more preferably 2 占 퐉 or more, particularly preferably 3 占 퐉 or more from the viewpoint of enhancing the insulating performance of the insulating layer 100 . The thickness T of the insulating layer 100 indicates the dimension of the insulating layer 100 between the first conductor layer 210 and the second conductor layer 220. The thickness T of the first conductor layer 210 or the second conductor layer 220, But does not indicate the dimension of the insulating layer 100 at a position where the second conductor layer 220 is not present. The thickness T of the insulating layer 100 is generally set such that the major surface 210U of the first conductor layer 210 opposed to the main surface 220D of the second conductor layer 220, And also coincides with the depth of the via hole 110.

The top diameter Lt of the via hole 110 of the insulating layer 100 included in the specific printed wiring board 300 is usually 35 占 퐉 or less, preferably 33 占 퐉 or less, particularly preferably 32 占 퐉 or less. The specific printed wiring board 300 includes the first conductor layer 210 and the second conductor layer 220 because it includes the insulating layer 100 having the via hole 110 having a small top diameter Lt It is possible to promote miniaturization of the wiring. The lower limit of the top diameter Lt of the via hole 110 is preferably 3 mu m or more, more preferably 10 mu m or more, particularly preferably 15 mu m or more, from the viewpoint of easily forming the via hole 110, Or more.

The taper ratio Lb / Lt (%) of the via hole 110 of the insulating layer 100 included in the specific printed wiring board 300 is usually 80% to 100%. The specific printed wiring board 300 includes the insulating layer 100 having the via hole 110 having a good shape with a high taper ratio Lb / Lt. Therefore, the specific printed wiring board 300 can increase the conduction reliability between the first conductor layer 210 and the second conductor layer 220 in general.

The haloing distance Wb from the edge 170 of the via bottom 120 of the via hole 110 of the insulating layer 100 included in the specific printed wiring board 300 is usually 5 占 퐉 or less, 4 mu m or less. The specific printed wiring board 300 is formed such that the haloing distance Wb from the edge 170 of the via bottom 120 is so small that the peeling of the insulating layer 100 from the first conductor layer 210 small. Therefore, the specific printed wiring board 300 can increase the reliability of conduction between the first conductor layer 210 and the second conductor layer 220 in general.

The halo ingot Hb against the bottom radius Lb / 2 of the via hole 110 of the insulating layer 100 included in the specific printed wiring board 300 is generally 35% or less, preferably 33% or less, More preferably, it is 31% or less. The specific printed wiring board 300 has such a small halo ratio Hb with respect to the bottom radius Lb / 2 and thus the separation of the insulating layer 100 from the first conductor layer 210 is small. The specific printed wiring board 300 including the insulating layer 100 having a small halo grains Hb generally has reliability of conduction between the first conductor layer 210 and the second conductor layer 220 . The lower limit of the halo ratio Hb to the bottom radius (Lb / 2) is ideally zero, but is usually at least 5%.

The number of the via holes 110 included in the insulating layer 100 included in the specific printed wiring board 300 may be one, or may be two or more. When the insulating layer 100 has two or more via holes 110, a part thereof may satisfy the requirements (ii) to (v), but all of them satisfy the requirements (ii) to (v) desirable. It is also preferable that, for example, five via holes 110 randomly selected from the insulating layer 100 satisfy the requirements (ii) to (v) on average.

The above-mentioned specific printed wiring board 300 can be realized by forming the insulating layer 100 with the cured product of the resin composition layer of the present invention. At this time, the via-bottom 120 and the via-top 130 of the via-hole 110 formed in the insulating layer 100 may have any plane shape, but are generally circular or elliptical, and preferably circular.

A printed wiring board such as a specific printed wiring board can be produced by, for example, using a resin sheet and performing the manufacturing method including the following steps (I) to (III).

(I) A step of laminating a resin sheet on the inner layer substrate so that the resin composition layer is bonded to the inner layer substrate.

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

(III) A step of forming via holes in the insulating layer.

The " inner layer substrate " used in the step (I) is a member to be a substrate of a 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. Normally, as the inner layer substrate, one having a conductor layer on one side or both sides thereof is used. Then, an insulating layer is formed on the conductor layer. Such a conductor layer may be patterned to function as, for example, a circuit. An inner layer substrate having a conductor layer formed as a circuit on one side or both sides of the substrate may be referred to as an " inner layer circuit substrate ". Further, an intermediate product to which the insulating layer and / or the conductor layer is to be further formed when manufacturing the printed wiring board is also included in the " inner layer substrate ". If the printed wiring board is a component built-in circuit board, an inner-layer board containing components may be used.

The lamination of the inner layer substrate and the resin sheet can be performed, for example, by heating and pressing the resin sheet to the inner layer substrate on the support side, and bringing the resin composition layer into contact with the inner layer substrate. Examples of the member for heating and pressing the resin sheet to the inner layer substrate (hereinafter also referred to as " hot pressing member ") include a heated metal plate (SUS hard plate) or a metal roll (SUS roll) . Further, it is preferable to press the heat-press member through an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently follow the surface unevenness of the inner layer substrate, instead of directly pressing the heat-press member to the resin sheet.

The lamination of the inner layer substrate and the resin sheet may be carried out, for example, by a vacuum laminating method. In the vacuum laminating method, the heat-pressing temperature is preferably in the range of 60 占 폚 to 160 占 폚, more preferably 80 占 폚 to 140 占 폚, the heat pressing pressure is preferably 0.098 MPa to 1.77 MPa, Is in the range of 0.29 MPa to 1.47 MPa, and the heat pressing time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. The lamination is preferably performed under a reduced pressure of 26.7 hPa or less.

The lamination can be performed by a commercially available vacuum laminator. As a commercially available vacuum laminator, for example, a vacuum pressurized laminator manufactured by Meiji Seisakusho Co., Ltd., a baking applicator manufactured by Nikko Materials Co., Ltd., and a vacuum type vacuum laminator are available.

After lamination, the laminated resin sheet may be subjected to smoothing treatment under atmospheric pressure (at atmospheric pressure), for example, by pressing the hot press member on the support side. The pressing condition of the smoothing treatment may be the same as the conditions of the hot pressing of the laminate. The smoothing process can be performed by a commercially available laminator. The lamination and the smoothing process may be performed continuously using the commercially available vacuum laminator.

In the step (II), the resin composition layer is thermally cured to form an insulating layer. The thermosetting conditions of the resin composition layer are not particularly limited, and the conditions employed when forming the insulating layer of the printed wiring board may be arbitrarily used.

For example, the thermosetting condition of the resin composition layer varies depending on the kind of the resin composition and the like, but the curing temperature is usually in the range of 120 to 240 占 폚 (preferably in the range of 150 to 220 占 폚, more preferably 170 ° C to 200 ° C), and 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 thermosetting the resin composition layer. For example, before the resin composition layer is thermally cured, the resin composition layer is heated at a temperature of generally 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) May be preliminarily heated for usually 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, further preferably 15 minutes to 100 minutes).

In the step (III), a via hole is formed in the insulating layer. Examples of the method of forming the via-hole include laser light irradiation, etching, and mechanical drilling. Among them, haloing phenomenon is likely to occur in irradiation of laser light. Therefore, from the viewpoint of effectively utilizing the effect of inhibiting the haloing phenomenon, laser irradiation is preferable.

Such laser light irradiation can be performed, for example, by using a laser processing machine having a laser light source such as a carbon dioxide gas laser, a YAG laser, or an excimer laser as a light source. As the laser processing machine that can be used, for example, a CO ₂ laser processing machine "LC-2k212 / 2C" manufactured by VIA MECHANICS, 605GTWIII (-P) manufactured by Mitsubishi Denki K.K., a laser processing machine manufactured by Matsushita Iowa Systems Co., .

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

Incidentally, the support may be removed between the step (I) and the step (II), or between the step (II) and the step (III) or may be removed after the step (III). Among them, it is preferable to remove after the step (III) of forming the via-hole in the insulating layer from the viewpoint of further suppressing the occurrence of the depressed portion. For example, when the support is peeled off after the via hole is formed in the insulating layer by irradiation with laser light, the via hole having a good shape can be easily formed.

The manufacturing method of the 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) may be carried out according to various methods used in the production of printed wiring boards. When 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 between the step (IV) and the step (V).

Step (IV) is a step of roughening the insulating layer. The procedure and conditions of the roughening treatment are not particularly limited and arbitrary procedures and conditions used for forming the insulating layer of the printed wiring board can be adopted. For example, the swelling treatment with a swelling liquid, the coarsening treatment with an oxidizing agent, and the neutralization treatment with a neutralizing liquid can be carried out in this order to roughen the insulating layer.

The swelling liquid is not particularly limited, and examples thereof include an alkali solution, a surfactant solution, and the like, preferably an alkali solution. As the alkali solution, sodium hydroxide solution and potassium hydroxide solution are more preferable. Examples of commercially available swelling liquids include "Swelling Deep Sucrygan G P" and "Swelling Deep Sucralgan SBU" manufactured by Atotech Japan Co., Ltd. The swelling liquid may be used singly or in combination of two or more in an arbitrary ratio. The swelling treatment by the swelling liquid is not particularly limited, and can be performed, for example, by immersing the swelling liquid at 30 캜 to 90 캜 for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin in the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in the swelling liquid at 40 占 폚 to 80 占 폚 for 5 minutes to 15 minutes.

The oxidizing agent is not particularly limited, and for example, an alkaline permanganic acid solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide can be mentioned. The oxidizing agent may be used singly or in combination of two or more in an arbitrary 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 at 60 캜 to 80 캜 for 10 minutes to 30 minutes. The concentration of the permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as "Concentrate Compact CP" manufactured by Atotech Japan Co., Ltd., and "Dozing Solution Securegan's P".

As the neutralization solution, an acidic aqueous solution is preferable, and commercially available products include, for example, " Reduction Solution Securigans P " manufactured by Atotech Japan Co., The neutralizing liquid may be used singly or in combination of two or more in an arbitrary ratio. The treatment with the neutralizing liquid can be performed by immersing the treated surface subjected to the roughening treatment with the oxidizing agent in a neutralizing solution at 30 ° C to 80 ° C for 5 minutes to 30 minutes. From the standpoint of workability and the like, it is preferable to immerse the object subjected to the roughening treatment with an oxidizing agent in a neutralizing solution at 40 to 70 캜 for 5 to 20 minutes.

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 at least one metal selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium . The conductor layer may be a single metal layer or an alloy layer. Examples of the alloy layer include a layer formed of an alloy of two or more kinds of metals (for example, a nickel-chromium alloy, a copper-nickel alloy, and a copper-titanium alloy) selected from the above-mentioned group. Among them, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper single metal layers are preferable from the viewpoints of versatility of the conductor layer formation, cost and ease of patterning. Or an alloy layer of a nickel-chromium alloy, a copper-nickel alloy, or a copper-titanium alloy. Further, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper single metal layers; Or an alloy layer of a nickel-chromium alloy is more preferable, and a single-ended metal layer is particularly preferable.

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

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

The conductor layer may be formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating the surface of the insulating layer by a technique such as a semi-custom method or a pull-to-body method. Above all, from the viewpoint of simplicity of production, it is preferable to form it by the semi-specific method.

Hereinafter, an example in which the conductor layer is formed by the semi- First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Then, a mask pattern for exposing a part of the plating seed layer corresponding to the desired wiring pattern is formed on the formed plating seed layer. A metal layer is formed on the exposed plating seed layer by electrolytic plating, and then the mask pattern is removed. Thereafter, an unnecessary plating seed layer is removed by etching or the like, and a conductor layer having a desired wiring pattern can be formed.

Furthermore, if necessary, the multilayer printed wiring board may be produced by repeating the formation of the insulating layer and the conductor layer by the steps (I) to (V).

[14. Semiconductor device]

The semiconductor device of the present invention includes the above-mentioned printed wiring board. Such a semiconductor device can be manufactured by using a printed wiring board.

Examples of the semiconductor device include various semiconductor devices provided in an electric product (e.g., a computer, a mobile phone, a digital camera and a television) and a vehicle (e.g., a motorcycle, an automobile, a tank, .

The semiconductor device can be manufactured, for example, by mounting a component (semiconductor chip) in a conductive portion of a printed wiring board. The "conduction point" is a "point for transmitting electrical signals on the printed wiring board", and may be a surface or a buried point. Further, as the semiconductor chip, an electric circuit element using a semiconductor material can be arbitrarily used.

The method of mounting the semiconductor chip at the time of manufacturing the semiconductor device is not particularly limited as long as the semiconductor chip effectively functions. Examples of the mounting method include a wire bonding mounting method, a flip chip mounting method, a mounting method using a bumpless buildup layer (BBUL), a mounting method using an anisotropic conductive film (ACF), a mounting method using a nonconductive film (NCF) . Here, the "mounting method using the bumpless buildup layer (BBUL)" refers to a "mounting method in which the semiconductor chip is directly buried in the concave portion of the printed wiring board to connect the semiconductor chip and the wiring on the printed wiring board.

Example

Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to the following examples. In the following description, " parts " and "% " representing quantities mean " part by mass " and "% by mass ", respectively, unless otherwise specified. In addition, the operations described below were carried out under normal ambient temperature and normal pressure unless otherwise specified.

[Explanation of inorganic filler]

≪ Method of measuring average particle diameter of inorganic filler >

, 0.1 g of a dispersing agent (" SN9228 " manufactured by Sanbopo Co., Ltd.) and 10 g of methyl ethyl ketone were weighed in a vial bottle and dispersed by ultrasonic waves for 20 minutes. The particle diameter distribution of the inorganic filler was measured on a volumetric basis by a batch cell method using a laser diffraction particle diameter distribution measuring device ("SALD-2200" manufactured by Shimadzu Corporation). From the obtained particle diameter distribution, the average particle diameter of the inorganic filler was calculated as the intermediate diameter.

≪ Method for measuring specific surface area of inorganic filler &

The specific surface area of the inorganic filler was measured using a BET full automatic specific surface area measuring apparatus ("Macsorb HM-1210" manufactured by Mau Tec Corporation).

<Types of inorganic fillers>

Inorganic filler 1: 100 parts of spherical silica ("UFP-30" manufactured by Denki Kagakuko Co., Ltd., average particle diameter: 0.078 μm, specific surface area: 30.7 m 2 / g) was added N-phenyl-3-aminopropyltrimethoxysilane Manufactured by Shin-Etsu Chemical Co., Ltd., KBM573).

Inorganic filler 2: 100 parts of spherical silica ("SC2500SQ" manufactured by Admatechs Co., Ltd., average particle diameter 0.77 μm, specific surface area 5.9 m 2 / g) was added N-phenyl-3-aminopropyltrimethoxysilane Manufactured by Kokusa Kogyo Co., Ltd., KBM573).

[Example 1: Preparation of Resin Composition 1]

, 6 parts of a biscylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Kagaku Co., Ltd., epoxy equivalent: about 185), 5 parts of a naphthalene type epoxy resin (ESN475V manufactured by Shin Nitetsu Sumikin Kagaku, epoxy equivalent weight of about 332) , 15 parts of resin ("YL7760" manufactured by Mitsubishi Kagaku Co., Ltd., epoxy equivalent of about 238), 2 parts of cyclohexane type epoxy resin ("ZX1658GS" manufactured by Mitsubishi Kagaku Corp., epoxy equivalent weight of 135) 2 parts of a solvent mixture of 20 parts by weight of solvent naphtha and 10 parts by weight of cyclohexanone was dissolved by heating in a mixed solvent of 20 parts by weight of solvent naphtha and 10 parts by weight of cyclohexanone, . The resulting solution was cooled to room temperature. Then, 5 parts of a naphthol-based curing agent (aromatic hydrocarbon resin represented by Chemical Formula 5, "SN395", manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., hydroxyl equivalent of 107) as an ingredient (B), 5 parts of an active ester type curing agent 6 parts of an inorganic filler 1 (trade name: EXB-8000L-65TM, an activator group equivalent of about 220, and a nonvolatile component 65% by mass of toluene: MEK solution 1: 1), 50 parts of an amine- Pyridine (DMAP)) were mixed and uniformly dispersed in a high-speed rotary mixer to obtain a mixture. This mixture was filtered with a cartridge filter (&quot; SHP020 &quot; manufactured by ROKITECHNO) to obtain Resin Composition 1.

[Example 2: Preparation of Resin Composition 2]

The same operation as in Example 1 was carried out except that the kinds and amounts of reagents used were changed as shown in Table 1 to prepare Resin Composition 2. Specific changes from Example 1 are as follows.

("ZX1059", manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., epoxy equivalent weight: about 169, bisphenol A type and bisphenol type epoxy resin) were used in place of 2 parts of cyclohexane type epoxy resin ("ZX1658GS" manufactured by Mitsubishi Kagaku Co., (1: 1 mixture of F type) and 2 parts of naphthylene ether type epoxy resin ("EXA-7311-G4" manufactured by DIC Corporation, epoxy equivalent weight: about 213)

In place of 2 parts of a phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Kagaku Co., Ltd., a 1: 1 solution of cyclohexanone: methyl ethyl ketone (MEK) having a nonvolatile component of 30 mass%, Mw = 35000) 2 parts of a 1: 1 solution of cyclohexanone: methyl ethyl ketone (MEK), Mw = 44000) and 30 parts by mass of a nonvolatile component of YL7500BH30 manufactured by Mitsubishi Kagaku Co., Ltd. were used.

As the component (B), a phenol-based curing agent (an aromatic hydrocarbon resin represented by the formula (4)) was used instead of 5 parts of a naphthol-based curing agent ("SN395" manufactured by Shinnitetsu Sumikin Kagaku Co., Quot; GRA13H &quot;, and hydroxyl equivalent 75) were used.

[Comparative Example 1] Preparation of Resin Composition 3 [

The same operation as in Example 1 was carried out except that the kinds and amounts of the reagents to be used were changed as shown in Table 1 to prepare Resin Composition 3. Specific changes from Example 1 are as follows.

("ZX1059", manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., epoxy equivalent weight: about 169, bisphenol A type and bisphenol type epoxy resin) were used in place of 2 parts of cyclohexane type epoxy resin ("ZX1658GS" manufactured by Mitsubishi Kagaku Co., (1: 1 mixture of F type) and 2 parts of naphthylene ether type epoxy resin ("EXA-7311-G4" manufactured by DIC Corporation, epoxy equivalent weight: about 213)

In place of 2 parts of a phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Kagaku Co., Ltd., a 1: 1 solution of cyclohexanone: methyl ethyl ketone (MEK) having a nonvolatile component of 30 mass%, Mw = 35000) 2 parts of a 1: 1 solution of cyclohexanone: methyl ethyl ketone (MEK), Mw = 44000) and 30 parts by mass of a nonvolatile component of YL7500BH30 manufactured by Mitsubishi Kagaku Co., Ltd. were used.

A cresol novolac-based curing agent ("LA-3018-50P" manufactured by DIC Corporation) as the component (E) was used instead of 5 parts of the naphthol-based curing agent (SN395 manufactured by Shinnitetsu Sumikin Kagaku Co., , A hydroxyl group equivalent of about 151, and a non-volatile component 50% in 2-methoxypropanol solution).

[Comparative Example 2: Preparation of Resin Composition 4]

The same operation as in Example 1 was carried out except that the kinds and amounts of the reagents to be used were changed as shown in Table 1 to prepare Resin Composition 4. Specific changes from Example 1 are as follows.

("LA-3018-50P" manufactured by DIC Co., Ltd.) containing triazine skeleton as the component (E) was used instead of 5 parts of the naphthol-based curing agent (SN395 manufactured by Shinnitetsu Sumikin Kagaku Co., Hydroxyl group equivalent of about 151, and non-volatile component 50% of 2-methoxypropanol solution).

Instead of using 50 parts of the inorganic filler 1, 80 parts of the inorganic filler 2 was used.

[Comparative Example 3: Preparation of Resin Composition 5]

The same operation as in Example 1 was carried out except that the kinds and amounts of the reagents used were changed as shown in Table 1 to prepare Resin Composition 5. Specific changes from Example 1 are as follows.

(SN485, manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., hydroxyl equivalent weight of about 215) 4 as a component (E) was used instead of 5 parts of a naphthol-based curing agent (SN395 manufactured by Shinnitetsu Sumikin Kagaku Co., And 4 parts of a cresol novolak-based curing agent containing a triazine skeleton ("LA-3018-50P" manufactured by DIC Corporation, hydroxyl equivalent equivalent of about 151 and 50% non-volatile component of 2-methoxypropanol solution) were used.

[Comparative Example 4: Preparation of Resin Composition 6]

The same operation as in Example 1 was carried out except that the kinds and amounts of reagents to be used were changed as shown in Table 1 to prepare Resin Composition 6. Specific changes from Example 1 are as follows.

5 parts of a naphthol-based curing agent ("SN395", manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., hydroxyl group equivalent 107) and 5 parts of an active ester curing agent "EXB-8000L-65TM" (1: 1 solution of toluene: MEK in mass%), and further adding a triazine skeleton-containing cresol novolac curing agent ("LA-3018-50P" manufactured by DIC Co., 151, a non-volatile component 50% solution in 2-methoxypropanol).

Instead of using 50 parts of the inorganic filler 1, 80 parts of the inorganic filler 2 was used.

[Composition of resin composition]

The components used in the preparation of Resin Compositions 1 to 6 and the compounding amount thereof (parts by mass of nonvolatile matter) are shown in Table 1 below. The abbreviations in the following table are as follows.

Content of curing agent: Content of curing agent to 100 mass% of resin component in resin composition.

Content of active ester-based curing agent: Content of active ester-based curing agent relative to 100 mass% of the resin component in the resin composition.

Content of inorganic filler: Content of inorganic filler to 100 mass% of non-volatile component in resin composition.

[Production of Resin Sheet]

A polyethylene terephthalate film (&quot; Lumirror80 &quot;, manufactured by Toray Industries, Inc., thickness: 38 mu m, softening point 130 DEG C) subjected to release treatment with an alkyd resin-based releasing agent (AL-5, manufactured by Lintec Corporation) was prepared as a support.

Each of the resin compositions 1 to 6 was uniformly coated on a support with a die coater so that the thickness of the resin composition layer after drying was 10 占 퐉 and dried at 70 占 폚 to 95 占 폚 for 2 minutes to form a resin composition layer did. Subsequently, a roughened surface of a polypropylene film ("ALPAN MA-411" manufactured by Oji-Fiftech Co., Ltd., thickness 15 μm) as a protective film was bonded to the surface of the resin composition layer not bonded to the support. Thus, a resin sheet A having a support, a resin composition layer, and a protective film in this order was 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 (&quot; MCD-25MJ &quot; manufactured by Mitsutoyo Corporation).

[Evaluation of via hole after laser via processing]

Using the resin sheet A prepared using each of the resin compositions 1 to 6, an insulating layer having via holes was formed by the following method, and the via holes were evaluated.

<Preparation of sample for evaluation>

(1) Preparation of inner layer substrate:

A glass cloth base epoxy resin double-sided copper clad laminate (HL832NSF LCA, thickness: 3 mu m, substrate thickness: 0.15 mm, manufactured by Mitsubishi Gas Kagaku Co., Ltd., size of 255 x 340 mm) having copper foil layers on both surfaces was prepared as the inner layer substrate.

(2) Laminate of resin sheet:

The protective film was peeled from the resin sheet A to expose the resin composition layer. Layer laminate was laminated on both surfaces of the inner layer substrate so that the resin composition layer was in contact with the inner layer substrate by using a vacuum pressurizing laminator (Niko Materials &quot; CVP700, 2 step buildup laminator &quot; The laminate was subjected to pressure reduction for 30 seconds to adjust the air pressure to 13 hPa or less, followed by compression at 130 DEG C and pressure of 0.74 MPa for 45 seconds. Then, hot pressing was performed at 120 DEG C and a pressure of 0.5 MPa for 75 seconds.

(3) Thermal curing of the resin composition layer:

Thereafter, the inner-layer substrate laminated with the resin sheet was placed in an oven at 100 캜, heated for 30 minutes, transferred to an oven at 180 캜 and heated for 30 minutes to thermally cure the resin composition layer to form an insulating layer. The thickness of the insulating layer was 10 mu m. Thus, a cured substrate A having a support, an insulating layer, an inner layer substrate, an insulating layer, and a support in this order was obtained.

(4) Laser via processing:

Laser light was irradiated to the insulating layer through a support using a CO ₂ laser processing machine ("605GTWIII (-P)" manufactured by Mitsubishi Denki K.K.) To form a plurality of via holes having a top diameter (diameter) . The irradiation conditions of the laser beam were 1 mm in mask diameter, 16 占 퐏 in pulse width, 0.2 mJ / shot in energy, 2 in number of shots, and burst mode (10 kHz).

(5) Harmonizing treatment:

After forming a via hole in the insulating layer, the support was peeled off to obtain a via-processed substrate A having the insulating layer, the innerlayer substrate, and the insulating layer in this order. Thereafter, the via processed substrate A was subjected to a desmear treatment as a roughening treatment. As the desmear treatment, the following wet desmear treatment was carried out.

(Wet desmear treatment)

The via-processed substrate A was immersed in a swelling liquid (aqueous solution of "Swelling Deep Securigans P", diethylene glycol monobutyl ether and sodium hydroxide, manufactured by Atotech Japan Co., Ltd.) at 60 ° C for 10 minutes, (Concentrate Compact CP manufactured by Tek Japan Co., Ltd .; an aqueous solution having a potassium permanganate concentration of about 6% and a sodium hydroxide concentration of about 4%) for 20 minutes at 80 ° C, and then a neutralization solution (Reduction Solution Sucury Gans P ", aqueous sulfuric acid solution) at 40 ° C for 5 minutes, and then dried at 80 ° C for 15 minutes. The via-processed substrate A subjected to the wet desmear treatment is referred to as a coarsened substrate A.

&Lt; Measurement of dimensions of via holes before harmonic treatment >

As a sample, a via-processed substrate A before the roughening treatment was prepared. The via-processed substrate A was subjected to a cross-section observation using an FIB-SEM composite device ("SMI3050SE" manufactured by SII Nanotechnology Co., Ltd.). More specifically, using an FIB (focused ion beam), the insulating layer was scraped so that a cross section extending parallel to the thickness direction of the insulating layer and passing through the center of the via bottom of the via hole appeared. These cross sections were observed by SEM (scanning electron microscope), and the top diameter and bottom diameter of via holes were measured from the observed images.

The above-mentioned measurement was carried out at five randomly selected via holes. Then, the average of the measured values of the measured diameters of the via holes of the five holes was adopted as the top diameter Lt1 of the via-hole of the sample. The average of the measured values of the bottom diameters of the via holes measured at five places was used as the bottom diameter Lb1 of the via-hole of the sample.

&Lt; Measurement of Dimension of via Hole after Hardening >

As a sample, a harmonized substrate A was used in place of the via-processed substrate A. Except for the above, the same operation as in < Measurement of dimensions of via holes before harmonization treatment > was carried out to measure the top diameter (Lt2) and bottom diameter (Lb2) of via holes after the coarsening treatment.

&Lt; Measurement of haloing distance before harmonic treatment >

The via-processed substrate A was observed with an optical microscope (&quot; KH8700 &quot; Specifically, the insulating layer around the via-hole was observed at the top of the via-processed substrate A using an optical microscope (CCD). This observation was made by focusing the optical microscope on the via-top. As a result of the observation, a donut-shaped halo portion having an insulating layer turned to white from the edge of the via-hole of the via-hole was observed around the via-hole. The radius (r1) of the via-hole of the via-hole (corresponding to the inner radius of the hollow portion) and the outer radius (r2) of the halo portion are measured from the observed image, and the radius r1 and the radius r2 (R2-r1) as the haloing distance from the edge of the via-top of the measurement point.

The above-mentioned measurement was carried out at five randomly selected via holes. Then, the average of the measured values of the haloing distances of the five via holes measured was adopted as the haloing distance Wt from the edge of the via-top of the sample.

&Lt; Dimension measurement of haloing distance after harmonic treatment >

The cross-section of the coarsened substrate A was observed using an FIB-SEM composite device ("SMI3050SE" manufactured by SII Nanotechnology Co., Ltd.). More specifically, using an FIB (focused ion beam), the insulating layer was scraped so that a cross section parallel to the thickness direction of the insulating layer and passing through the center of the via bottom of the via hole appeared. These cross sections were observed by SEM (scanning electron microscope). As a result of observation, a gap portion formed by peeling the insulating layer from the copper foil layer of the innerlayer substrate was observed successively from the edge of the via bottom. The distance r3 from the observed image to the edge of the via bottom at the center of the via bottom (corresponding to the inner radius of the halo portion) r3 and the distance from the center of the via bottom to the far side end of the via portion R4) of the distance r4 between the distance r4 and the distance r4 is calculated as the haloing distance from the edge of the via bottom of the measurement point.

The above-described measurement was carried out at five randomly selected via holes. Then, the average of the measured values of the haloing distances of the five via holes measured was adopted as the haloing distance Wb from the edge of the via bottom of the sample.

[result]

The evaluation results of the above Examples and Comparative Examples are shown in Table 2 below.

In Table 2, the taper ratio indicates the ratio &quot; Lb1 / Lt1 &quot; of the bottom diameter Lt1 of the via-hole before the harmonic treatment to the bottom diameter Lb1. When the taper ratio Lb1 / Lt1 was 75% or more, the via processability was judged as "good". When the taper ratio (b1 / Lt1) was less than 75%, the via processability was judged as "poor".

In Table 2, the halo ingot (Ht) before the roughening treatment is the ratio of the haloing distance (Wt) from the edge of the via-top before the roughening treatment to the radius (Lt1 / 2) of the via- Wt / (Lt1 / 2) &quot;. If the halo ingot Ht is 35% or less, the halo ing evaluation is judged as "good". If the halo ingot Ht is higher than 35%, the halo ing evaluation is judged as "bad".

In Table 2, the halo ingot (Hb) after the roughening treatment is the ratio of the haloing distance Wb from the edge of the via bottom after the roughening treatment to the radius Lb2 / 2 of the via bottom of the via hole after the roughening treatment Wb / (Lb2 / 2) &quot;. If the halo ingot Hb is 35% or less, the halo ing evaluation is judged as "good". If the halo ingot Ht is greater than 35%, the halo ing evaluation is judged as "bad".

[Review]

As can be seen from Table 2, in the embodiment, a via hole having a large taper ratio can be formed in the insulating layer while forming an insulating layer using a resin composition layer having a thickness of 10 占 퐉. From these results, it was confirmed that the resin composition layer of the present invention can realize an insulating layer capable of forming a via-hole having a good shape even if the thickness is thin.

As can be seen from Table 2, in the examples, the insulating layer is formed by using the resin composition layer having a thickness of 10 占 퐉, and the haloing ratio of the halo portion due to the formation of the via hole is small. From these results, it was confirmed that the insulating layer capable of suppressing the haloing phenomenon can be realized by the resin composition layer of the present invention even if the thickness is thin.

Particularly, when the thickness of the via hole is 35 占 퐉 or less and the taper ratio of the via hole is 80% or more and the thickness of the via hole is 35 占 퐉 or less as obtained in Examples 1 and 2, An insulating layer having a haloing distance of 5 占 퐉 or less and a haloing ratio of 35% or less to the bottom radius of the via hole has not been realized in the past. Therefore, the reason why such an insulating layer can be realized is remarkable technical significance in a recent printed wiring board in which it is desired to make the insulating layer thinner.

In the first to second embodiments, although concrete results are not shown in the case where a conductor layer is formed on the insulating layer of the coarse substrate A, the results of the above-described embodiments show that a conductor layer is formed on the insulating layer of the coarse substrate A It is possible for a person skilled in the art to clearly understand that a specific printed wiring board satisfying the requirements (i) to (v) can be obtained.

In Examples 1 to 2, even when the components (D) and (F) were not contained, it was confirmed that the results were the same as those of the above-mentioned Examples although there were differences in the degree.

100 insulating layer
The surface of the insulating layer on the opposite side of the 100U conductor layer
110 via hole
120 Via Bottom
120C Center of Via Bottom
130 Via Tower
140 Half a pig
150 Via hole Via top edge
160 Edge on the outer circumference side of the halo portion
170 Edge of Via Bottom of Via Hole
180 gap portion
190 End portion on the outer peripheral side of the gap portion
200 inner layer substrate
210 conductor layer (first conductor layer)
220 second conductor layer
300 printed wiring board
Bottom Diameter of Lb via Hole
Lt Via hole top diameter
T insulation layer thickness
Walt Via the edge of Via Pagoda
Wb The haloing distance from the edge of the via bottom

Claims (15)

As the resin composition layer having a thickness of 15 mu m or less including the resin composition,
Wherein the resin composition comprises (A) an epoxy resin, (B) an aromatic hydrocarbon resin containing an aromatic ring as a monocyclic or condensed ring having two or more hydroxyl groups, and (C) an inorganic filler having an average particle diameter of 100 nm or less. Resin composition layer. As the resin composition layer having a thickness of 15 mu m or less including the resin composition,
Wherein the resin composition comprises (A) an epoxy resin, (B) an aromatic hydrocarbon resin containing an aromatic ring as a monocyclic or condensed ring having two or more hydroxyl groups, and (C) an inorganic filler having a specific surface area of 15 m2 / Resin composition layer. The resin composition layer according to claim 1 or 2, wherein the component (B) is represented by the following formula (1) or (2).
[Chemical Formula 1]

(In the general formula (1), R ⁰ independently represents a divalent hydrocarbon group, and n1 represents an integer of 0 to 6)
(2)

(In the formula (2), R ¹ to R ⁴ each independently represent a hydrogen atom or a monovalent hydrocarbon group) The resin composition layer according to claim 1 or 2, wherein the component (B) is represented by the following formula (3) or (4).
(3)

(In the general formula (3), n2 represents an integer of 0 to 6)
[Chemical Formula 4]

(In the formula (4), R ¹ to R ⁴ each independently represent a hydrogen atom or a monovalent hydrocarbon group) The resin composition layer according to claim 1 or 2, wherein the amount of the component (B) is 5% by mass to 50% by mass with respect to 100% by mass of the resin component in the resin composition. The resin composition layer according to 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 according to claim 1 or 2, which is for forming an insulating layer for forming a conductor layer. The resin composition layer according to claim 1 or 2, for forming an interlayer insulating layer of a printed wiring board. The resin composition layer according to claim 1 or 2, wherein the resin composition layer is for forming an insulating layer having a via-hole of a diameter of 35 mu m or less. A support,
A resin sheet comprising the resin composition layer according to claim 1 or 2 formed on a support. A printed wiring board comprising an insulating layer formed of a cured product of the resin composition layer according to claim 1 or 2. A printed wiring board comprising a first conductor layer, a second conductor layer, and an insulating layer formed between the first conductor layer and the second conductor layer,
The thickness of the insulating layer is 15 占 퐉 or less,
Wherein the insulating layer has a via hole with a top diameter of 35 mu m or less,
The taper ratio of the via hole is 80% or more,
The haloing distance from the edge of the bottom of the via hole is 5 占 퐉 or less,
And the haloing ratio to the bottom radius of the via-hole is 35% or less. The printed wiring board according to claim 12, wherein the haloing ratio to the bottom radius of the via-hole is 5% or more. A semiconductor device comprising the printed wiring board according to claim 11. A semiconductor device comprising the printed wiring board according to claim 12 or claim 13.

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