CN108864654B - Resin composition layer - Google Patents

Resin composition layer Download PDF

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CN108864654B
CN108864654B CN201810436857.6A CN201810436857A CN108864654B CN 108864654 B CN108864654 B CN 108864654B CN 201810436857 A CN201810436857 A CN 201810436857A CN 108864654 B CN108864654 B CN 108864654B
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resin composition
mass
component
resin
composition layer
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CN108864654A (en
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鹤井一彦
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Ajinomoto Co Inc
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Ajinomoto Co Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/006—Additives being defined by their surface area
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Production Of Multi-Layered Print Wiring Board (AREA)

Abstract

The subject of the invention is to provide a resin composition layer which can obtain an insulating layer capable of inhibiting a halo phenomenon even though the thickness is small and forming a through hole with a good shape. The solution of the present invention is a resin composition layer comprising a resin composition having a thickness of 15 [ mu ] m or less, wherein the resin composition comprises: (A) an epoxy resin; (B) An aromatic hydrocarbon resin containing an aromatic ring which is an aromatic ring having 2 or more hydroxyl groups as a single ring or a condensed ring; and (C) has an average particle diameter of 100nm or less and 15m 2 An inorganic filler having at least one of specific surface areas of not less than/g.

Description

Resin composition layer
Technical Field
The present invention relates to a resin composition layer. The present invention further relates to a resin sheet comprising the resin composition layer; and a printed wiring board and a semiconductor device including an insulating layer formed of a cured product of the resin composition layer.
Background
In recent years, further thinning of printed wiring boards has been advanced in order to achieve miniaturization of electronic devices. Accordingly, miniaturization of wiring circuits in inner-layer substrates is advancing. For example, patent document 1 describes a resin sheet (adhesive film) containing a support and a resin composition layer, which can accommodate fine wiring.
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2014-36051.
Disclosure of Invention
Problems to be solved by the invention
The present inventors have studied a technique of making a resin composition layer of a resin sheet thinner in order to further miniaturize and thin electronic devices. As a result of the study, the present inventors found that when a thinner resin composition layer is applied to the insulating layer, a halo (insulating) phenomenon occurs after the formation of the via hole. Here, the halo phenomenon refers to a phenomenon in which the resin of the insulating layer is discolored around the through hole. Such a halo phenomenon is generally generated due to deterioration of the resin around the through hole. Further, it is known that if the insulating layer in which the halo phenomenon occurs is roughened, resin in the insulating layer portion in which the halo phenomenon occurs (hereinafter, sometimes referred to as "halo portion") is eroded during the roughening treatment, and interlayer peeling occurs between the insulating layer and the inner layer substrate.
Further, the present inventors have found that when a thin resin composition layer is applied to an insulating layer, it is difficult to control the shape of a via hole, and it is difficult to obtain a via hole having a good shape. Here, the "good" shape of the through hole means that the taper ratio (t-case ratio) of the through hole is close to 1. In addition, the taper ratio of the through hole refers to the ratio of the bottom diameter to the top diameter of the through hole.
The problems described above are all problems that occur for the first time by making the thickness of the resin composition layer thin, and are new problems that have not been known in the past. From the viewpoint of improving the conduction reliability between layers of a printed wiring board, it is desired to solve these problems.
The present invention has been made in view of the above problems, and an object of the present invention is to provide a resin composition layer which can obtain an insulating layer that can suppress a halo phenomenon even when the thickness is small and can form a through hole of a good shape; the present invention also aims to provide a resin sheet comprising the aforementioned resin composition layer; a printed wiring board comprising a thin insulating layer capable of suppressing a halo phenomenon and forming a through hole of a good shape; and a semiconductor device including the printed wiring board.
Means for solving the problems
The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that the above problems can be solved by a resin composition comprising, in combination: (A) an epoxy resin; (B) An aromatic hydrocarbon resin containing an aromatic ring which is an aromatic ring having 2 or more hydroxyl groups as a single ring or a condensed ring; and (C) has an average particle diameter of 100nm or less and 15m 2 The present invention has been completed by the above-mentioned finding.
Namely, the present invention includes the following:
[1] a resin composition layer having a thickness of 15 [ mu ] m or less and containing a resin composition,
wherein the resin composition comprises: (A) an epoxy resin; (B) An aromatic hydrocarbon resin containing an aromatic ring which is an aromatic ring having 2 or more hydroxyl groups as a single ring or a condensed ring; and (C) an inorganic filler having an average particle diameter of 100nm or less;
[2] a resin composition layer having a thickness of 15 [ mu ] m or less and containing a resin composition,
wherein the resin composition comprises: (A) an epoxy resin; (B) An aromatic hydrocarbon resin containing an aromatic ring which is an aromatic ring having 2 or more hydroxyl groups as a single ring or a condensed ring; and (C) a specific surface area of 15m 2 An inorganic filler material of/g or more;
[3] the resin composition layer according to [1] or [2], wherein the component (B) is represented by the following formula (1) or (2),
Figure 994122DEST_PATH_IMAGE001
(in the formula (1), R 0 Each independently represents a 2-valent hydrocarbon group, and n1 represents an integer of 0 to 6. )
Figure 911262DEST_PATH_IMAGE002
(in the formula (2), R 1 ～R 4 Each independently represents a hydrogen atom or a 1-valent hydrocarbon group.)；
[4] The resin composition layer according to any one of [1] to [3], wherein the component (B) is represented by the following formula (3) or formula (4),
Figure 753316DEST_PATH_IMAGE003
(in the formula (3), n2 represents an integer of 0 to 6.)
Figure 148525DEST_PATH_IMAGE004
(in the formula (4), R 1 ～R 4 Each independently represents a hydrogen atom or a 1-valent hydrocarbon group. ) The method comprises the steps of carrying out a first treatment on the surface of the
[5] The resin composition layer according to any one of [1] to [4], wherein the amount of the component (B) is 5 to 50% by mass relative 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 relative to 100% by mass of the nonvolatile component in the resin composition;
[7] the resin composition layer according to any one of [1] to [6], wherein the resin composition layer is used for forming an insulating layer for forming a conductor layer (for forming an insulating layer for forming a conductor layer);
[8] the resin composition layer according to any one of [1] to [7], wherein the resin composition layer is used for forming an interlayer insulating layer of a printed wiring board;
[9] the resin composition layer according to any one of [1] to [8], wherein the resin composition layer is used for forming an insulating layer having a through hole with a top diameter of 35 μm or less;
[10] a resin sheet comprising: a support and the resin composition layer of any one of [1] to [9] provided on the support;
[11] A printed wiring board comprising an insulating layer formed of a cured product of the resin composition layer described in any one of [1] to [9 ];
[12] a printed wiring board including a first conductor layer, a second conductor layer, and an insulating layer formed between the first conductor layer and the second conductor layer, wherein,
the thickness of the insulating layer is 15 μm or less,
the insulating layer has a through hole with a top diameter of 35 μm or less,
the taper ratio of the through hole is 80% or more,
the halo distance of the via hole from the bottom edge is below 5 μm,
the halo ratio of the through hole relative to the bottom radius is below 35%;
[13] the printed wiring board according to [12], wherein a halo ratio of the through hole with respect to a bottom radius is 5% or more;
[14] a semiconductor device comprising the printed wiring board of any one of [11] to [13 ].
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, there can be provided a resin composition layer which can obtain an insulating layer capable of suppressing a halo phenomenon even if the thickness is thin and capable of forming a well-shaped through hole; a resin sheet comprising the aforementioned resin composition layer may also be provided; a printed wiring board comprising a thin insulating layer capable of suppressing a halo phenomenon and forming a through hole of a good shape; and a semiconductor device including the printed wiring board.
Drawings
Fig. 1 is a cross-sectional view schematically showing an insulating layer and an inner layer substrate obtained by curing a resin composition layer according to a first embodiment of the present invention;
fig. 2 is a plan view (plan view) schematically showing a surface of an insulating layer on the opposite side of a conductor layer, the surface being obtained by curing a resin composition layer according to a first embodiment of the present invention;
fig. 3 is a cross-sectional view schematically showing the roughened insulating layer and the inner substrate obtained by curing the resin composition layer according to the first embodiment of the present invention;
fig. 4 is a schematic cross-sectional view of a printed wiring board according to a second embodiment of the present invention.
Detailed Description
The present invention will be described in detail with reference to the following embodiments and examples. However, the present invention is not limited to the embodiments and examples described below, and may be arbitrarily modified and implemented within the scope of the claims and their equivalents.
In the following description, the "resin component" of the resin composition refers to a component other than the inorganic filler among the nonvolatile components contained in the resin composition.
[1. Outline of resin composition layer ]
The resin composition layer of the present invention is a thin resin composition layer having a thickness of a predetermined value or less. Further, the resin composition contained in the resin composition layer of the present invention comprises:
(A) An epoxy resin;
(B) An aromatic hydrocarbon resin containing an aromatic ring which is an aromatic ring (an aromatic ring in the form of a single ring or a condensed ring) having 2 or more hydroxyl groups as a single ring or a condensed ring; and
(C) Has an average particle diameter of 100nm or less and 15m 2 An inorganic filler having at least one of specific surface areas of not less than/g.
Accordingly, any one of the first resin composition and the second resin composition described below may be included in the resin composition contained in the resin composition layer of the present invention.
The first resin composition comprises (A) an epoxy resin; (B) An aromatic hydrocarbon resin containing an aromatic ring which is an aromatic ring having 2 or more hydroxyl groups as a single ring or a condensed ring; and (C) an inorganic filler having an average particle diameter of 100nm or less.
The second resin composition comprises (A) an epoxy resin; (B) An aromatic hydrocarbon resin containing an aromatic ring which is an aromatic ring having 2 or more hydroxyl groups as a single ring or a condensed ring; (C) a specific surface area of 15m 2 An inorganic filler material of not less than/g.
By using such a resin composition layer, a thinner insulating layer can be obtained. Thus, the following desired effects of the present invention can be obtained: a well-shaped via hole can be formed in the insulating layer obtained while suppressing the halo phenomenon.
[2. ] (A) component: epoxy resin
Examples of the epoxy resin as the component (a) include: a bisxylenol (bispyrinol) 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, a triphenol type epoxy resin, a naphthol novolac (phenolic novolac) type epoxy resin, a tert-butyl catechol type epoxy resin, a naphthalene type epoxy resin, a naphthol type epoxy resin, an anthracene type epoxy resin, a glycidylamine type epoxy resin, a glycidyl ester type epoxy resin, a cresol novolac (cresol novolac) type epoxy resin, a biphenyl type epoxy resin, a linear aliphatic epoxy resin, an epoxy resin having a butadiene structure, a cycloaliphatic epoxy resin, a heterocyclic type epoxy resin, a spiro ring-containing epoxy resin, a cyclohexane type epoxy resin, a cyclohexanedimethanol type epoxy resin, a naphthylene ether type epoxy resin, a trimethylol type epoxy resin, a tetraphenylethane type epoxy resin, and the like. The epoxy resin may be used alone in an amount of 1 kind, or may be used in an amount of 2 or more kinds.
The resin composition preferably contains, as the (a) epoxy resin, an epoxy resin having 2 or more epoxy groups in 1 molecule. From the viewpoint of significantly obtaining the desired effect of the present invention, the proportion of the epoxy resin having 2 or more epoxy groups in 1 molecule is preferably 50 mass% or more, more preferably 60 mass% or more, particularly preferably 70 mass% or more, with respect to 100 mass% of the nonvolatile component of the (a) epoxy resin.
Epoxy resins include epoxy resins that are liquid at a temperature of 20 ℃ (sometimes referred to as "liquid epoxy resins" hereinafter) and epoxy resins that are solid at a temperature of 20 ℃ (sometimes referred to as "solid epoxy resins"). The resin composition may contain only a liquid epoxy resin or only a solid epoxy resin as the epoxy resin (a), and preferably contains a liquid epoxy resin and a solid epoxy resin in combination. As the (a) epoxy resin, by using a liquid epoxy resin and a solid epoxy resin in combination, the flexibility of the resin composition layer can be improved, or the breaking strength of the cured product of the resin composition layer can be improved.
The liquid epoxy resin is preferably a liquid epoxy resin having 2 or more epoxy groups in 1 molecule, and more preferably an aromatic liquid epoxy resin having 2 or more epoxy groups in 1 molecule. Here, the "aromatic-based" epoxy resin refers to an epoxy resin having an aromatic ring in its molecule.
As the liquid epoxy resin, bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, glycidyl amine type epoxy resin, and epoxy resin having a butadiene structure are preferable; more preferred are bisphenol a type epoxy resins, bisphenol F type epoxy resins and cyclohexane type epoxy resins.
Specific examples of the liquid epoxy resin include: "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC; "828US", "jER828EL", "825", "EPIKOTE 828EL" by Mitsubishi chemical corporation (bisphenol A type epoxy resin); "jER807", "1750" manufactured by mitsubishi chemical company (bisphenol F type epoxy resin); "jER152" (phenol novolac epoxy resin) manufactured by mitsubishi chemical company; "630", "630LSD" (glycidyl amine type epoxy resin) manufactured by Mitsubishi chemical corporation; "ZX1059" manufactured by Nippon iron gold chemical Co., ltd. (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Co., ltd; "CELLOXIDE 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by macrocellulite corporation; "PB-3600" manufactured by Daxiu corporation (epoxy resin having a butadiene structure); "ZX1658" and "ZX1658GS" (liquid 1, 4-glycidyl cyclohexane type epoxy resin) manufactured by Nippon Ten Kagaku Kogyo Co., ltd. These may be used alone or in combination of 1 or more than 2.
As the solid epoxy resin, a solid epoxy resin having 3 or more epoxy groups in 1 molecule is preferable, and an aromatic solid epoxy resin having 3 or more epoxy groups in 1 molecule is more preferable.
As the solid epoxy resin, there are preferable a binaphthol-type epoxy resin, a naphthalene-type tetrafunctional epoxy resin, a cresol novolac-type epoxy resin, a dicyclopentadiene-type epoxy resin, a triphenol-type epoxy resin, a naphthol-type epoxy resin, a biphenyl-type epoxy resin, a naphthylene ether-type epoxy resin, an anthracene-type epoxy resin, a bisphenol a-type epoxy resin, a bisphenol AF-type epoxy resin, a tetraphenylethane-type epoxy resin; more preferred are a binaphthol-type epoxy resin, a naphthalene-type epoxy resin, a bisphenol AF-type epoxy resin, and a naphthylene ether-type epoxy resin.
Specific examples of the solid epoxy resin include: "HP4032H" (naphthalene type epoxy resin) manufactured by DIC Co; "HP-4700", "HP-4710" manufactured by DIC corporation (naphthalene type tetrafunctional epoxy resin); "N-690" (cresol novolac type epoxy resin) manufactured by DIC Co., ltd; "N-695" (cresol novolac type epoxy resin) manufactured by DIC Co., ltd; "HP-7200" manufactured by DIC corporation (dicyclopentadiene type epoxy resin); "HP-7200HH", "HP-7200H", "EXA-7311-G3", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin) manufactured by DIC; "EPPN-502H" (triphenol type epoxy resin) manufactured by Japanese chemical Co., ltd; "NC7000L" manufactured by Japanese chemical Co., ltd. (naphthol novolac type epoxy resin); "NC3000H", "NC3000L", "NC3100" (biphenyl type epoxy resin) manufactured by japan chemical medicine corporation; "ESN475V" manufactured by Nippon iron and gold chemical Co., ltd. (naphthalene type epoxy resin); "ESN485" (naphthol novolac epoxy resin) manufactured by Nippon iron gold chemical Co., ltd; "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi chemical corporation; "YX4000HK" (Bixylenol type epoxy resin) manufactured by Mitsubishi chemical corporation; "YX8800" (anthracene-type epoxy resin) manufactured by mitsubishi chemical company; "PG-100", "CG-500" manufactured by Osaka gas chemical Co., ltd; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi chemical corporation; "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi chemical corporation; "jER1010" (solid bisphenol a type epoxy resin) manufactured by mitsubishi chemical company; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by mitsubishi chemical company, and the like. These may be used alone or in combination of 1 or more than 2.
When a liquid epoxy resin and a solid epoxy resin are used in combination as the (a) epoxy resin, the ratio of the amounts thereof (liquid epoxy resin: solid epoxy resin) is preferably 1 in terms of mass ratio: 1 to 1: 20. more preferably 1: 2-1: 15. particularly preferably 1:5 to 1:13. by making the amount ratio of the liquid epoxy resin and the solid epoxy resin within the above-described range, the desired effect of the present invention can be remarkably obtained. Further, when the resin sheet is used in the form of a resin sheet, it is generally possible to impart moderate tackiness. In addition, when the resin sheet is used in the form of a resin sheet, sufficient flexibility is obtained and the operability is improved. Further, a cured product having sufficient breaking strength can be obtained.
(A) The epoxy equivalent of the epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, still more preferably 110 to 1000. When the epoxy equivalent is within this range, the crosslink density of the cured product of the resin composition layer becomes sufficient, and an insulating layer having a small surface roughness can be provided. The epoxy equivalent means the mass of the resin containing 1 equivalent of epoxy group. The epoxy equivalent can be measured in accordance with JIS K7236.
From the viewpoint of significantly obtaining the desired effect of the present invention, the weight average molecular weight (Mw) of the (a) epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and further preferably 400 to 1500.
The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by Gel Permeation Chromatography (GPC).
From the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability, the amount of the (a) epoxy resin in the resin composition is preferably 10 mass% or more, more preferably 20 mass% or more, and still more preferably 30 mass% or more, relative to 100 mass% of the resin component in the resin composition. The upper limit of the content of the epoxy resin is preferably 90 mass% or less, more preferably 85 mass% or less, particularly preferably 80 mass% or less, from the viewpoint of remarkably obtaining the desired effect of the present invention.
[3 ] (B) component: aromatic hydrocarbon resin containing aromatic ring which is aromatic ring having 2 or more hydroxyl groups as single ring or condensed ring ]
The resin composition contains, as component (B), an aromatic hydrocarbon resin containing an aromatic ring having 2 or more hydroxyl groups. In general, the component (B) can react with the epoxy resin (a) through the hydroxyl group of the aromatic ring, and thus can function as a curing agent for curing the resin composition. Thus, the halo phenomenon can be suppressed by the action of the component (B).
Here, the term "aromatic ring" includes any of an aromatic ring in a single ring form such as a benzene ring, and an aromatic ring in a condensed ring form such as a naphthalene ring. From the viewpoint of significantly obtaining the desired effect of the present invention, the number of carbon atoms per 1 of the aforementioned aromatic rings contained in the component (B) is preferably 6 or more, more preferably 14 or less, and still more preferably 10 or less.
Examples of the aromatic ring include: benzene rings, naphthalene rings, anthracene rings, and the like. The aromatic hydrocarbon resin may have 1 kind or 2 or more kinds of aromatic rings contained in 1 molecule.
At least one of the aromatic rings contained in the aromatic hydrocarbon resin as the component (B) has 2 or more hydroxyl groups per 1 aromatic ring. The number of hydroxyl groups per 1 aromatic ring is preferably 3 or less, particularly preferably 2, from the viewpoint of remarkably obtaining the desired effect of the present invention.
(B) The number of aromatic rings having 2 or more hydroxyl groups per 1 molecule of the component is usually 1 or more, preferably 2 or more, more preferably 3 or more, from the viewpoint of significantly obtaining the desired effect of the present invention. The upper limit is not particularly limited, but is preferably 6 or less, more preferably 5 or less, from the viewpoint of suppressing steric hindrance and improving reactivity with the epoxy resin.
Examples of suitable components (B) include aromatic hydrocarbon resins represented by the following formula (1) and aromatic hydrocarbon resins represented by the following formula (2);
Figure 962898DEST_PATH_IMAGE005
Figure 785360DEST_PATH_IMAGE006
。
in the formula (1), R 0 Each independently represents a hydrocarbyl group of valence 2. The hydrocarbon group having a valence of 2 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 2-valent hydrocarbon group is usually 1 or more, and from the viewpoint of significantly obtaining the desired effect of the present invention, it is preferably 3 or more, 6 or more, or 7 or more. The upper limit of the number of carbon atoms may be preferably 20 or less, 15 or less, or 10 or less from the viewpoint of significantly obtaining the desired effect of the present invention.
As R 0 Specific examples of (a) include the following hydrocarbon groups;
Figure 52393DEST_PATH_IMAGE007
。
in the formula (1), n1 represents an integer of 0 to 6. 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 remarkably obtaining the desired effect of the present invention.
If the aromatic hydrocarbon resin represented by the formula (1) is used, the halo phenomenon can be suppressed particularly effectively.
In the formula (2), R 1 ～R 4 Each independently represents a hydrogen atom or a 1-valent hydrocarbon group. The hydrocarbon group having a valence of 1 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, from the viewpoint of significantly obtaining the desired effect of the present invention, an aliphatic hydrocarbon group is preferable, a saturated aliphatic hydrocarbon group is more preferable, and a chain saturated aliphatic hydrocarbon group is particularly preferable. The number of carbon atoms of the 1-valent 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 significantly obtaining the desired effect of the present invention. As R 1 ～R 4 In the preferred embodiment of (a),there may be mentioned: a hydrogen atom; alkyl groups such as methyl, ethyl, propyl, butyl, and hexyl. If the aromatic hydrocarbon resin represented by the formula (2) is used, peeling of the halo portion caused by erosion at the time of roughening treatment can be suppressed particularly effectively.
Among them, the aromatic hydrocarbon resin represented by the following formula (3) and the aromatic hydrocarbon resin represented by the following formula (4) are particularly preferable as the component (B). In the formula (3), n2 represents an integer defined as n1 in the formula (1), and the preferable range is the same. In addition, R in formula (4) 1 ～R 4 R in the formula (2) 1 ～R 4 The meanings are the same;
Figure 313611DEST_PATH_IMAGE008
Figure 982489DEST_PATH_IMAGE009
。
examples of the commercial product of the aromatic hydrocarbon resin represented by the formula (3) include naphthol curing agent "SN395" manufactured by the new japanese iron and gold chemical company represented by the following formula (5). In the formula (5), n3 represents 2 or 3. Further, as a commercial product of the aromatic hydrocarbon resin represented by the formula (4), for example, a phenol-based curing agent "GRA13H" manufactured by the general chemical industry company;
Figure 975853DEST_PATH_IMAGE010
。
the aromatic hydrocarbon resin as the component (B) may be used alone in an amount of 1 kind or in an amount of 2 or more kinds.
The hydroxyl equivalent of the component (B) is preferably 50g/eq or more, more preferably 60g/eq or more, still more preferably 70g/eq or more, and is preferably 200g/eq or less, more preferably 150g/eq or less, particularly preferably 120g/eq or less, from the viewpoint of improving the crosslinking density of the insulating layer as a cured product of the resin composition layer and remarkably obtaining the desired effect of the present invention. Hydroxyl equivalent refers to the mass of the resin containing 1 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, preferably 50% by mass or less, more preferably 40% by mass or less, 30% by mass or 20% by mass or less, relative to 100% by mass of the resin component in the resin composition. By making the amount of the component (B) within the aforementioned range, the halo phenomenon can be effectively suppressed.
The amount of the component (B) is preferably 5% by mass or more, more preferably 8% by mass or more, particularly preferably 10% by mass or more, and preferably 100% by mass or less, more preferably 50% by mass or less, particularly preferably 30% by mass or less, relative to 100% by mass of the epoxy resin (a). By making the amount of the component (B) within the aforementioned range, the halo phenomenon can be effectively suppressed.
When the number of epoxy groups of the epoxy resin (a) is 1, the number of hydroxyl groups of the component (B) is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.3 or more, preferably 2 or less, more preferably 1.5 or less, still more preferably 1 or less, and particularly preferably 0.5 or less. The "(a) epoxy resin epoxy number" means a value obtained by dividing the mass of the nonvolatile component of the component (a) in the resin composition by the epoxy equivalent weight and summing up the total. The "(hydroxyl number of component (B)" means a value obtained by dividing the mass of the nonvolatile component (B) existing in the resin composition by the hydroxyl equivalent weight, and summing up the total. When the hydroxyl number of the component (B) is within the above range when the epoxy number of the epoxy resin (A) is 1, the halo phenomenon can be effectively suppressed.
[4 ] (C) component: has an average particle diameter of 100nm or less and 15m 2 Inorganic filler having at least one of specific surface areas of not less than/g]
The resin composition contains an inorganic filler as the component (C). With the inorganic filler, the coefficient of thermal expansion of the cured product of the resin composition layer can be reduced, and thus an insulating layer in which reflow warp is suppressed can be obtained. The inorganic filler as component (C) has an average particle diameter of 100nm or less and 15m 2 At least one of specific surface areas of/g or more. As inorganic filler materialBy using the component (C) having at least one of the average particle diameter and the specific surface area in the above-described range in combination with the component (B), an insulating layer in which a well-shaped through hole can be formed can be realized.
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 oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate, calcium zirconate, zirconium phosphate, etc. Among these, silica is particularly suitable. Examples of the silica include: amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, and the like. In addition, spherical silica is preferable as silica. The inorganic filler may be used alone or in combination of 1 or more than 2.
The average particle diameter of the component (C) is usually 100nm or less, preferably 90nm or less, more preferably 80nm or less from the viewpoint of forming the insulating layer as a thin layer and from the viewpoint of controlling the shape of the through hole and realizing a good shape. The lower limit of the average particle diameter is not particularly limited, but is preferably 50nm or more, 60nm or more, or 70nm or more. Examples of the commercial products of the inorganic filler having the average particle diameter include "UFP-30" and "UFP-40" manufactured by electric chemical industry Co., ltd.
The average particle size of the inorganic filler material can be determined by a laser diffraction-scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is prepared by a laser diffraction scattering particle size distribution measuring apparatus on a volume basis, and the median particle size is measured as the average particle size. For the measurement sample, a sample obtained by dispersing an inorganic filler in methyl ethyl ketone by ultrasonic waves can be preferably used. As the laser diffraction scattering type particle size distribution measuring apparatus, "LA-500" manufactured by horiba corporation, and "SALD-2200" manufactured by Shimadzu corporation may be used.
The specific surface area of the component (C) is usually 15m from the viewpoint of easy control of the shape of the through hole and realization of a good shape 2 Above/g, preferably 20m 2 Preferably 30m or more per gram 2 And/g. In addition, since the component (C) having a large specific surface area has a small particle diameter, the insulating layer can be made thin. The upper limit is not particularly limited, but is preferably 60m 2 Per gram of less than 50m 2 /g or less than 40m 2 And/g or less. The specific surface area of the inorganic filler can be determined by the BET method.
From the viewpoint of improving moisture resistance and dispersibility, the inorganic filler as the component (C) is preferably treated with a surface treatment agent. Examples of the surface treatment agent include: fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilane-nitrogen compounds, titanate coupling agents, and the like. In addition, 1 kind of the surface treating agent may be used alone, or 2 or more kinds may be used in any combination.
Examples of the commercial products of the surface treatment agent include: "KBM403" from Xinyue chemical industry Co., ltd. (3-glycidoxypropyl trimethoxysilane), "KBM803" from Xinyue chemical industry Co., ltd. (3-mercaptopropyl trimethoxysilane), "KBE903" from Xinyue chemical industry Co., ltd. (3-aminopropyl triethoxysilane), "KBM573" from Xinyue chemical industry Co., ltd. (hexamethyldisilazane), "KBM103" from Xinyue chemical industry Co., ltd. (phenyl trimethoxysilane), "KBM-4803" from Xinyue chemical industry Co., ltd. (long chain epoxy type silane coupling agent), and "KBM-7103" from Xinyue chemical industry Co., ltd. (3, 3-trifluoropropyl trimethoxysilane) and the like.
The degree of the surface treatment with the surface treatment agent is preferably within a predetermined range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, the inorganic filler is preferably surface-treated with 0.2 to 5 parts by mass of a surface-treating agent, preferably 0.2 to 3 parts by mass, and preferably 0.3 to 2 parts by mass, based on 100 parts by mass of the inorganic filler.
The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the carbon amount per unit surface area of the inorganic filler is preferably 0.02mg/m 2 The above, more preferably 0.1mg/m 2 The above, and more preferably 0.2mg/m 2 The above. On the other hand, from the viewpoint of suppressing the rise in melt viscosity of the resin varnish in sheet form, it is preferably 1mg/m 2 Hereinafter, more preferably 0.8mg/m 2 The concentration of the active ingredient is preferably 0.5mg/m 2 The following is given.
The amount of carbon per unit surface area of the inorganic filler may be measured after the surface-treated inorganic filler is washed with a solvent (e.g., methyl Ethyl Ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent may be added to the inorganic filler surface-treated with the surface treating agent, and ultrasonic washing may be performed at 25 ℃ for 5 minutes. The supernatant was removed, and after drying the solid component, the carbon amount per unit surface area of the inorganic filler was measured using a carbon analyzer. As the carbon analyzer, EMIA-320V manufactured by horiba corporation may be used.
The amount of the component (C) in the resin composition is preferably 30 mass% or more, more preferably 35 mass% or more, and still more preferably 40 mass% or more, based on 100 mass% of the nonvolatile component in the resin composition, from the viewpoint of reducing the dielectric loss tangent of the insulating layer. In addition, in the case where the resin composition layer containing such a large amount of the inorganic filler is a thin layer, it has been difficult to form a through hole of a good shape, and in particular, if the amount of the inorganic filler is 50 mass% or more relative to 100 mass% of the nonvolatile components in the resin composition, it is particularly difficult to form a through hole of a good shape. Therefore, from the viewpoint of effectively utilizing the advantages of the present invention that a through hole having a good shape can be formed (which is a matter of particular difficulty in the past as described above), the amount of the component (C) is preferably 50 mass% or more, particularly preferably 54 mass% or more, relative to 100 mass% of the nonvolatile component in the resin composition. The upper limit of the amount of the component (C) is preferably 90 mass% or less, more preferably 85 mass% or less, further preferably 80 mass% or less, or 75 mass% or less, relative to 100 mass% of the nonvolatile component in the resin composition, from the viewpoint of improving the mechanical strength of the insulating layer.
[5 ] (D) Components: 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: phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, polyetheretherketone resin, polyester resin, and the like. Among them, the phenoxy resin is preferable from the viewpoint of remarkably obtaining the desired effect of the present invention and the viewpoint of obtaining an insulating layer having a small surface roughness and particularly excellent adhesion to a conductor layer. Further, the thermoplastic resin may be used alone of 1 kind, or may be used in combination of 2 or more kinds.
Examples of the phenoxy resin include phenoxy resins having 1 or more kinds of skeletons selected from bisphenol a skeletons, bisphenol F skeletons, bisphenol S skeletons, bisphenol acetophenone skeletons, phenol skeletons, biphenyl skeletons, fluorene skeletons, dicyclopentadiene skeletons, norbornene skeletons, naphthalene skeletons, anthracene skeletons, adamantane skeletons, terpene skeletons, and trimethylcyclohexane skeletons. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group and an epoxy group.
Specific examples of the phenoxy resin include: "1256" and "4250" both made by Mitsubishi chemical corporation (phenoxy resins each having a bisphenol A skeleton); "YX8100" (phenoxy resin containing bisphenol S skeleton) manufactured by Mitsubishi chemical corporation; "YX6954" manufactured by Mitsubishi chemical corporation (phenoxy resin containing bisphenol acetophenone skeleton); "FX280" and "FX293" manufactured by Nippon Kagaku Co., ltd; "YL7500BH30", "YX6954BH30", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290" and "YL7482" manufactured by Mitsubishi chemical corporation; etc.
Examples of the polyvinyl acetal resin include a polyvinyl formal resin and a polyvinyl butyral resin, and a polyvinyl butyral resin is preferable. Specific examples of the polyvinyl acetal resin include "Denka butyl 4000-2", "Denka butyl 5000-A", "Denka butyl 6000-C", "Denka butyl 6000-EP" manufactured by electric chemical industry Co; S-LEC BH series, BX series (e.g., BX-5Z), KS series (e.g., KS-1), BL series, BM series, manufactured by the water chemical industry Co., ltd; etc.
Specific examples of the polyimide resin include "RIKACOAT SN20" and "RIKACOAT PN20" manufactured by new japan physicochemical company. Specific examples of the polyimide resin include linear polyimides (polyimides described in JP 2006-37083A) obtained by reacting difunctional hydroxyl-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride, and modified polyimides such as polyimides containing a polysiloxane skeleton (polyimides described in JP 2002-12667A and JP 2000-319386A).
Specific examples of the polyamide-imide resin include "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by eastern spinning corporation. Specific examples of the polyamide-imide resin include modified polyamide-imides such as "KS9100" and "KS9300" (polyamide-imide containing a polysiloxane skeleton) manufactured by hitachi chemical company.
Specific examples of the polyethersulfone resin include "PES5003P" manufactured by sumitomo chemical company.
Specific examples of the polyphenylene ether resin include a low polyphenylene ether-styrene resin "OPE-2St 1200" manufactured by Mitsubishi gas chemical corporation.
Specific examples of polysulfone resins include polysulfones "P1700" and "P3500" manufactured by Solvay Advanced Polymers.
From the viewpoint of significantly obtaining the desired effect of the present invention, the weight average molecular weight (Mw) of the (D) thermoplastic resin is preferably 8,000 or more, more preferably 10,000 or more, particularly preferably 20,000 or more, 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 0.1 mass% or more, more preferably 0.5 mass% or more, still more preferably 1 mass% or more, preferably 15 mass% or less, still more preferably 12 mass% or less, still more preferably 10 mass% or less, based on 100 mass% of the resin component in the resin composition, from the viewpoint of significantly obtaining the desired effect of the present invention.
[6. ] (E) component: curing agent ]
The resin composition may further contain a curing agent (E) other than the component (B) as an optional component in addition to the above components.
As the curing agent for the component (E), a substance having an effect of curing the component (a) can be used. Examples of the curing agent (E) include: an active ester-based curing agent, a phenol (phenol) -based curing agent, a naphthol-based curing agent, a benzoxazine-based curing agent, a cyanate-based curing agent, a carbodiimide-based curing agent, and the like. In addition, 1 kind of the curing agent may be used alone, or 2 or more kinds may be used in combination. Among them, the active ester-based curing agent is preferable from the viewpoint of remarkably obtaining the desired effect of the present invention.
As the active ester-based curing agent, a compound having 1 or more active ester groups in 1 molecule can be used. Among them, as the active ester-based curing agent, compounds having 2 or more ester groups having high reactivity in 1 molecule, such as phenol esters (phenol esters), thiophenol esters (thiophenol esters), N-hydroxylamine esters, esters of heterocyclic hydroxyl compounds, and the like, are preferable. The active ester curing agent is preferably obtained by condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxyl compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester-based curing agent obtainable from a carboxylic acid compound and a hydroxyl compound is preferable, and an active ester-based curing agent obtainable from a carboxylic acid compound and a phenol (phenol) compound and/or a naphthol compound is more preferable.
Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.
Examples of the phenol compound or the naphthol compound include: hydroquinone, resorcinol, bisphenol a, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol a, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, alpha-naphthol, beta-naphthol, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, dicyclopentadiene type diphenol compounds, phenol novolac (phenol novolac), and the like. The "dicyclopentadiene type diphenol compound" herein means a diphenol compound obtained by condensing 2 molecules of phenol on 1 molecule of dicyclopentadiene.
Preferable specific examples of the active ester-based curing agent include: an active ester compound comprising a dicyclopentadiene type diphenol structure, an active ester compound comprising a naphthalene structure, an active ester compound comprising an acetylate of a phenol-formaldehyde resin, an active ester compound comprising a benzoylate of a phenol-formaldehyde resin. Among them, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene type diphenol structure are more preferable. The "dicyclopentadiene type diphenol structure" means a 2-valent structural unit formed from phenylene-dicyclopentylene (dicyclopentadienylene) -phenylene.
As commercial products of the active ester curing agent, active ester compounds containing dicyclopentadiene type diphenol structure include "EXB9451", "EXB9460S", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L-65TM", "EXB-8150-65T" (manufactured by DIC Co.); examples of the active ester compound having a naphthalene structure include "EXB9416-70BK" (manufactured by DIC Co.); examples of the active ester compound containing an acetylation compound of a phenol novolac resin include "DC808" (manufactured by mitsubishi chemical company); examples of the active ester compound containing a benzoyl compound of a phenol novolac resin include "YLH1026" (manufactured by Mitsubishi chemical corporation); examples of the active ester-based curing agent for the acetylation of phenol resins include "DC808" (manufactured by Mitsubishi chemical corporation); examples of the active ester-based curing agent for the benzoyl compound of the phenol novolac resin include "YLH1026" (manufactured by Mitsubishi chemical corporation), "YLH1030" (manufactured by Mitsubishi chemical corporation), "YLH1048" (manufactured by Mitsubishi chemical corporation); etc.
As the phenol-based curing agent and the naphthol-based curing agent, curing agents having a phenol (novolac) structure are preferable from the viewpoints of heat resistance and water resistance. In addition, from the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent is more preferable.
Specific examples of the phenol-based curing agent and the naphthol-based curing agent include: "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Ming He Chemicals; "NHN", "CBN", "GPH" manufactured by Japanese chemical Co., ltd; "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V", "SN375" manufactured by Nippon gold chemical company; "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500" manufactured by DIC; etc.
Specific examples of the benzoxazine-based curing agent include "HFB2006M" manufactured by Showa Polymer, and "P-d" and "F-a" manufactured by four chemical industries, inc.
Examples of the cyanate-based curing agent include: difunctional cyanate resins such as bisphenol a dicyanate, polyphenol cyanate, oligo (3-methylene-1, 5-phenylene cyanate), 4 '-methylenebis (2, 6-dimethylphenyl cyanate), 4' -ethylenediphenyl dicyanate, hexafluorobisphenol a dicyanate, 2-bis (4-cyanate-based) phenylpropane, 1-bis (4-cyanate-based phenylmethane), bis (4-cyanate-3, 5-dimethylphenyl) methane, 1, 3-bis (4-cyanate-phenyl-1- (methylethylene)) benzene, bis (4-cyanate-phenyl) sulfide, and bis (4-cyanate-phenyl) ether; polyfunctional cyanate resins derived from phenol novolac resins and cresol novolac resins and the like; prepolymers obtained by partially triazining these cyanate resins; etc. Specific examples of the cyanate-based curing agent include "PT30" and "PT60" manufactured by Lonza Japan (phenol novolac type multifunctional cyanate resin), "ULL-950S" (multifunctional cyanate resin), "BA230" and "BA230S75" (prepolymer in which part or all of bisphenol a dicyanate is triazinized to form a trimer).
Specific examples of the carbodiimide-based curing agent include "V-03", "V-07", which are manufactured by Nisshink chemical (Nisshinbo Chemical).
When the (E) curing agent is used, the amount of the (E) curing agent in the resin composition is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, still more preferably 1 mass% or more, preferably 20 mass% or less, still more preferably 15 mass% or less, still more preferably 12 mass% or less, relative to 100 mass% of the resin component in the resin composition, from the viewpoint of significantly obtaining the desired effect of the present invention.
In the case of using the (E) curing agent, the amount of the (E) curing agent in the resin composition is preferably 40 mass% or more, more preferably 50 mass% or more, particularly preferably 60 mass% or more, preferably 120 mass% or less, more preferably 100 mass% or less, particularly preferably 90 mass% or less, with respect to 100 mass% of the (B) component, from the viewpoint of significantly obtaining the desired effect of the present invention.
Further, when the number of epoxy groups of the epoxy resin (a) is 1, the number of active groups of the component (E) is preferably 0.1 or more, more preferably 0.2 or more, preferably 2 or less, more preferably 1.5 or less, still more preferably 1 or less, and particularly preferably 0.5 or less. The "active number of component (E)" is a value obtained by dividing the mass of the nonvolatile component of component (E) in the resin composition by the active group equivalent, and summing up the total. When the number of epoxy groups of the (a) epoxy resin is 1, the number of active groups of the (E) component is within the above-described range, whereby an insulating layer having particularly excellent mechanical strength can be obtained.
[7 ] (F) component: curing accelerator ]
The resin composition may further contain (F) a curing accelerator as an optional component in addition to the above components.
Examples of the curing accelerator include: phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, and the like. Among them, phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators are preferable, and amine-based curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators are more preferable. The curing accelerator may be used alone or in combination of 1 or more than 2.
Examples of the phosphorus-based curing accelerator include: triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphine thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphine thiocyanate, and the like, with triphenylphosphine and tetrabutylphosphonium decanoate being preferred.
Examples of the amine-based curing accelerator include: trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4, 6-tris (dimethylaminomethyl) phenol, 1, 8-diazabicyclo (5, 4, 0) -undecene and the like, preferably 4-dimethylaminopyridine and 1, 8-diazabicyclo (5, 4, 0) -undecene.
Examples of the imidazole-based curing accelerator include: 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1, 2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2, 4-diamino-6- [2' -methylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [2' -undecylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [2' -ethyl-4 ' -methylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [2' -methylimidazolyl- (1 ') ] -ethyl-s-triazine isocyanurate, 2-phenylimidazole isocyanurate adduct, and process for preparing the same, imidazole compounds such as 2-phenyl-4, 5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2, 3-dihydro-1H-pyrrolo [1,2-a ] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline and the like, and adducts of imidazole compounds and epoxy resins, preferably 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole.
As the imidazole-based curing accelerator, commercially available products can be used, and examples thereof include "P200-H50" manufactured by Mitsubishi chemical corporation.
Examples of the guanidine curing accelerator include: dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene, 1-methylguanidine, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1-dimethylbiguanide, 1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1- (o-tolyl) biguanide and the like, preferably dicyandiamide, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene.
Examples of the metal curing accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include cobalt (II) acetylacetonate, organic cobalt complexes such as cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, organic zinc complexes such as zinc (II) acetylacetonate, organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.
When the (F) curing accelerator is used, the amount of the (F) curing accelerator in the resin composition is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, still more preferably 0.1 mass% or more, preferably 3 mass% or less, still more preferably 2 mass% or less, still more preferably 1.5 mass% or less, relative to 100 mass% of the resin component of the resin composition, from the viewpoint of significantly obtaining the desired effect of the present invention.
[ 8..A component (G): any additives ]
The resin composition may contain, in addition to the above components, any additives as optional components. Examples of the additives include: an organic filler material; organocopper compounds, organozinc compounds, organocobalt compounds, and other organometallic compounds; resin additives such as flame retardants, thickeners, defoamers, leveling agents, adhesion imparting agents, and colorants; etc. These additives may be used alone in an amount of 1 or in an amount of 2 or more.
[9. Thickness of resin composition layer ]
The resin composition layer is a layer formed from the above resin composition and has a thickness of a predetermined value or less. The specific thickness of the resin composition layer is usually 15 μm or less, preferably 14 μm or less, and more preferably 12 μm or less. Conventionally, the thickness of a resin composition layer for forming an insulating layer of a printed wiring board is generally thicker than the above thickness. In contrast, the present inventors have found that when a resin composition layer having a general composition is formed into a thin layer as described above, such a thin resin composition layer causes problems such as occurrence of a halo phenomenon and difficulty in controlling the shape of a through hole, which have not been known heretofore. The resin composition layer of the present invention is provided as a thin layer as described above from the viewpoint of solving such a new problem and contributing to the thinning of a printed wiring board. The lower limit of the thickness of the resin composition layer is arbitrary, and may be, for example, 1 μm or more and 3 μm or more.
[10. Properties of the resin composition layer ]
By curing the resin composition layer of the present invention, a thinner insulating layer formed from the cured product of the resin composition layer can be obtained. The insulating layer may have a well-formed via hole formed therein. In addition, when a via hole is formed in the insulating layer, a halo phenomenon can be suppressed. These effects will be described below with reference to the drawings.
Fig. 1 is a cross-sectional view schematically showing an insulating layer 100 and an inner layer substrate 200 obtained by curing a resin composition layer according to a first embodiment of the present invention. Fig. 1 shows a cross section of the insulating layer 100 cut off on a plane parallel to the thickness direction of the insulating layer 100 through the center 120C of the bottom 120 of the through hole 110.
As shown in fig. 1, the insulating layer 100 according to the first embodiment of the present invention is a layer formed by curing a resin composition layer formed on an inner layer substrate 200 including a conductor layer 210, and is formed from a cured product of the resin composition layer. Further, a via hole 110 is formed on the insulating layer 100. The through-hole 110 is generally formed in a shape of a forward taper (tapered shape) having a diameter that increases as the surface 100U of the insulating layer 100 opposite to the conductor layer 210 is located, and a diameter that decreases as the surface of the insulating layer 210 is located, and preferably in a columnar shape having a constant diameter in the thickness direction of the insulating layer 100. The via 110 is typically formed as follows: a laser beam is irradiated onto the surface 100U of the insulating layer 100 on the opposite side of the conductor layer 210, and a part of the insulating layer 100 is removed.
The bottom of the via 110 on the side of the conductor layer 210 is appropriately referred to as "via bottom", and is denoted by reference numeral 120. Then, the diameter of the via bottom 120 is referred to as a bottom diameter Lb. In addition, an opening of the via 110 formed on the opposite side from the conductor layer 210 is appropriately referred to as "via top", denoted by reference numeral 130. Then, the diameter of the via top 130 is referred to as the top diameter Lt. In general, the via bottom 120 and the via top 130 are formed in a circular planar shape as viewed from the thickness direction of the insulating layer 100, but may be elliptical. In the case where the planar shapes of the via bottom 120 and the via top 130 are elliptical, the bottom diameter Lb and the top diameter Lt thereof represent the major diameters of the ellipses, respectively.
At this time, the taper ratio Lb/Lt (%) obtained by dividing the bottom diameter Lb by the top diameter Lt is approximately 100%, the better the shape of the through hole 110. If the resin composition layer of the present invention is used, the shape of the through-hole 110 can be easily controlled, and thus the through-hole 110 having the taper ratio Lb/Lt close to 100% can be realized.
For example, under the conditions of a mask diameter of 1mm, a pulse width of 16. Mu.s, an energy of 0.2 mJ/shot, an emission number of 2, and a burst mode (10 kHz), the insulating layer 100 obtained by curing the resin composition layer by heating it at 100℃for 30 minutes and then at 180℃for 30 minutes is irradiated with CO 2 The laser light forms the through-hole 110 having the top diameter Lt of 30 μm±2 μm, and in this case, the taper ratio Lb/Lt of the through-hole 110 is preferably 60% to 100%, more preferably 70% to 100%, and particularly preferably 80% to 100%.
The taper ratio Lb/Lt of the through-hole 110 may be calculated from the bottom diameter Lb and the top diameter Lt of the through-hole 110. Further, the bottom diameter Lb and the top diameter Lt of the via hole 110 can be measured by cutting the insulating layer 100 using FIB (focused ion beam) so as to show a cross section parallel to the thickness direction of the insulating layer 100 and passing through the center 120C of the via hole bottom 120, and then observing the cross section with an electron microscope.
Fig. 2 is a plan view schematically showing a surface 100U of the insulating layer 100 on the opposite side to the conductor layer 210 (not shown in fig. 2) obtained by curing the resin composition layer according to the first embodiment of the present invention.
As shown in fig. 2, if the insulating layer 100 having the via hole 110 formed therein is observed, a halo portion 140 in which the insulating layer 100 is discolored may be observed around the via hole 110. The halo portion 140 may be formed by a halo phenomenon when the via hole 110 is formed, and is generally continuously formed from the via hole 110. In addition, in many cases, the halo portion 140 becomes a whitened portion.
By using the resin composition layer of the present invention, the aforementioned halo phenomenon can be suppressed. Therefore, the size of the halo portion 140 can be reduced, and the halo portion 140 can be desirably eliminated. The size of the halo portion 140 can be evaluated by the halo distance Wt of the via 110 from the edge 150 of the via top 130.
The edge 150 of the via top 130 corresponds to an edge portion on the inner peripheral side of the halo portion 140. The halo distance Wt from the edge 150 of the via top 130 represents the distance from the edge 150 of the via top 130 to the edge 160 on the outer peripheral side of the halo portion 140. The smaller the halo distance Wt from the edge 150 of the via top 130, the more effectively the halo phenomenon can be evaluated to be suppressed.
For example, the insulating layer 100 obtained by curing the resin composition layer by heating it at 100℃for 30 minutes and then at 180℃for 30 minutes under the conditions of a mask diameter of 1mm, a pulse width of 16. Mu.s, an energy of 0.2 mJ/emission, an emission number of 2, and a grouping mode (10 kHz) is irradiated with CO 2 The laser forms the via hole 110 with a top diameter Lt of 30 μm±2 μm, in which case the halo distance Wt from the edge 150 of the via top 130 is formed to be preferably 6 μm or less, more preferably 5 μm or less.
The halo distance Wt from the edge 150 of the via top 130 can be determined by observation with an optical microscope.
Further, as is clear from the study of the present inventors, in general, the larger the diameter of the through hole 110 is, the more easily the size of the halo portion 140 tends to be increased. Therefore, the degree of suppression of the halo phenomenon is evaluated by the ratio of the size of the halo portion 140 to the diameter of the through-hole 110. The evaluation can be performed, for example, by the halo ratio Ht of the via 110 with respect to the top radius Lt/2. Here, the top radius Lt/2 of the through-hole 110 refers to the radius of the through-hole top 130 of the through-hole 110. In addition, the halo ratio Ht of the via 110 relative to the top radius Lt/2 is the ratio of the halo distance Wt from the edge 150 of the via top 130 divided by the top radius Lt/2 of the via 110. The smaller the halo ratio Ht of the via 110 relative to the top radius Lt/2, the more effectively the halo phenomenon can be suppressed.
For example, the insulating layer 100 obtained by curing the resin composition layer by heating it at 100℃for 30 minutes and then at 180℃for 30 minutes under the conditions of a mask diameter of 1mm, a pulse width of 16. Mu.s, an energy of 0.2 mJ/emission, an emission number of 2, and a grouping mode (10 kHz) is irradiated with CO 2 Laser, forming a via hole 110 with a top diameter Lt of 30 μm±2 μm, in this case via hole 1The halo ratio Ht of 10 with respect to the top radius Lt/2 is preferably 45% or less, more preferably 40% or less, and still more preferably 35% or less.
The halo ratio Ht of the via 110 relative to the top radius Lt/2 may be calculated from the top diameter Lt of the via 110 and the halo distance Wt of the via 110 from the edge 150 of the via top 130.
Fig. 3 is a cross-sectional view schematically showing the roughened insulating layer 100 and the inner substrate 200 obtained by curing the resin composition layer according to the first embodiment of the present invention. Fig. 3 shows a cross section of the insulating layer 100 cut off in a plane parallel to the thickness direction of the insulating layer 100 through the center 120C of the via bottom 120 of the via 110.
As shown in fig. 3, if the insulating layer 100 where the via hole 110 is formed is roughened, the insulating layer 100 of the halo portion 140 may be peeled off from the conductor layer 210 to form a continuous gap portion 180 from the edge 170 of the via hole bottom 120. The gap portion 180 is typically formed by erosion of the halo portion 140 during the roughening process.
By using the resin composition layer of the present invention, as described above, the halo phenomenon can be suppressed. Therefore, the size of the halo portion 140 can be reduced, and the halo portion 140 can be desirably eliminated. Therefore, peeling of the insulating layer 100 from the conductor layer 210 can be suppressed, and thus the size of the gap portion 180 can be reduced.
The edge 170 of the through hole bottom 120 corresponds to an edge portion on the inner peripheral side of the gap portion 180. Therefore, the distance Wb from the edge 170 of the via bottom 120 to the end 190 on the outer peripheral side of the gap 180 (i.e., the end farther from the center 120C of the via bottom 120) corresponds to the dimension of the gap 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 a halo distance Wb of the via 110 from the edge 170 of the via bottom 120.
The extent of suppression of the formation of the gap portion 180 can be evaluated by the halo distance Wb from the edge 170 of the via bottom 120. Specifically, the smaller the halo distance Wb from the edge 170 of the via bottom 120, the more effectively the formation of the gap portion 180 can be estimated to be suppressed.
Further, the gap portion 180 is formed by peeling off the insulating layer 100 of the halo portion 140, and thus its size is related to the size of the halo phenomenon 140. Therefore, the smaller the halo distance Wb from the edge 170 of the via bottom 120, the more effectively the halo phenomenon can be evaluated to be suppressed.
For example, the insulating layer 100 obtained by curing the resin composition layer by heating it at 100℃for 30 minutes and then at 180℃for 30 minutes under the conditions of a mask diameter of 1mm, a pulse width of 16. Mu.s, an energy of 0.2 mJ/emission, an emission number of 2, and a grouping mode (10 kHz) is irradiated with CO 2 Laser, the via hole 110 with the top diameter Lt of 30 μm±2 μm is formed. Then, the resulting mixture was immersed in the swelling liquid at 60℃for 10 minutes, then immersed in the oxidizing agent solution at 80℃for 20 minutes, then immersed in the neutralizing liquid at 40℃for 5 minutes, and then dried at 80℃for 15 minutes. In the case of performing such roughening treatment, the halo distance Wb from the edge 170 of the via bottom 120 is formed to be preferably 60 μm or less, more preferably 50 μm or less, particularly preferably 40 μm or less.
The halo distance Wb from the edge 170 of the via bottom 120 can be measured by cutting the insulating layer 100 using FIB (focused ion beam) so as to show a cross section parallel to the thickness direction of the insulating layer 100 and passing through the center 120C of the via bottom 120, and then observing the cross section with an electron microscope.
Further, as is clear from the study of the present inventors, in general, the larger the diameter of the through hole 110 is, the more the size of the halo portion 140 tends to be large, and the size of the gap portion 180 tends to be large. Therefore, the degree of suppression of the halo phenomenon can be evaluated by the ratio of the size of the gap portion 180 to the diameter of the through hole 110, and further the degree of suppression of the formation of the gap portion 180 can be evaluated. For example, it can be evaluated by the halo ratio Hb of the via 110 relative to the bottom radius Lb/2. Here, the bottom radius Lb/2 of the through-hole 110 refers to the radius of the through-hole bottom 120 of the through-hole 110. In addition, the halo ratio Hb of the via 110 relative to the bottom radius Lb/2 is a ratio of the halo distance Wb from the edge 170 of the via bottom 120 divided by the bottom radius Lb/2 of the via 110. The smaller the halo ratio Hb of the via hole 110 with respect to the bottom radius Lb/2, the more effectively the formation of the gap portion 180 can be suppressed.
For example, the insulating layer 100 obtained by curing the resin composition layer by heating it at 100℃for 30 minutes and then at 180℃for 30 minutes under the conditions of a mask diameter of 1mm, a pulse width of 16. Mu.s, an energy of 0.2 mJ/emission, an emission number of 2, and a grouping mode (10 kHz) is irradiated with CO 2 Laser, the via hole 110 with the top diameter Lt of 30 μm±2 μm is formed. Then, the resulting mixture was immersed in the swelling liquid at 60℃for 10 minutes, then immersed in the oxidizing agent solution at 80℃for 20 minutes, then immersed in the neutralizing liquid at 40℃for 5 minutes, and then dried at 80℃for 15 minutes. When such roughening treatment is performed, the halo ratio Hb of the via hole 110 with respect to the bottom radius Lb/2 is preferably 60% or less, more preferably 50% or less, and still more preferably 40% or less.
The halo ratio Hb of the via 110 relative to the bottom radius Lb/2 may be calculated from the bottom diameter Lb of the via 110 and the halo distance Wb of the via 110 from the edge 170 of the via bottom 120.
In the process of manufacturing a printed wiring board, the through-hole 110 is generally formed in a state in which no additional conductor layer (not shown) is provided on the surface 100U of the insulating layer 100 on the opposite side to the conductor layer 210. Therefore, if the manufacturing process of the printed wiring board is clarified, it is clearly recognized that the via bottom 120 exists on the side of the conductor layer 210 and the via top 130 is opened on the side opposite to the conductor layer 210. However, in the completed printed wiring board, it is possible to provide conductor layers on both sides of the insulating layer 100. In this case, it may be difficult to distinguish the via bottom 120 and the via top 130 by a positional relationship with the conductor layer. However, in general, the top diameter Lt of the via top 130 is equal to or greater than the bottom diameter Lb of the via bottom 120. Thus, in the foregoing case, the via bottom 120 and the via top 130 can be distinguished by the size of the diameter.
The present inventors have speculated that the following is a structure in which the aforementioned effects are obtained from the resin composition layer of the present invention. However, the technical scope of the present invention is not limited by the structure described below.
Generally, when forming the via hole 110, energy such as heat, light, or the like is applied to a portion of the via hole 110 where the insulating layer 100 is to be formed. At this time, a part of the applied energy is transferred to the periphery of the portion where the through hole 110 is to be formed, and oxidation of the resin may occur. If such oxidation occurs, the resin deteriorates, possibly exhibiting a halo phenomenon. However, since the component (B) contains an aromatic ring having 2 or more hydroxyl groups, progress of oxidation reaction of the resin can be suppressed due to steric hindrance of the hydroxyl groups. Therefore, the insulating layer 100 obtained using the resin composition layer of the present invention can suppress the halo phenomenon.
As is clear 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 generally small. Since the particle diameter of the component (C) is small, energy applied to the insulating layer 100 can be transmitted well in the thickness direction of the insulating layer 100. For example, if thermal energy or optical energy is given to the face 100U of the insulating layer 100, the energy can be transferred in the thickness direction without causing a large attenuation. Accordingly, the through-hole 110 having a large taper ratio can be easily formed, and thus the shape of the through-hole 110 can be made good.
[11 use of resin composition layer ]
The resin composition layer of the present invention can be suitably used as a resin composition layer for insulation use. Specifically, the resin composition layer of the present invention can be suitably used as: a resin composition layer for forming an insulating layer of a printed wiring board (a resin composition layer for forming an insulating layer of a printed wiring board); and can thus be suitably used as: a resin composition layer for forming an interlayer insulating layer of a printed wiring board (a resin composition layer for forming an interlayer insulating layer of a printed wiring board). Further, the resin composition layer of the present invention can be suitably used as: a resin composition layer for forming an insulating layer (a resin composition layer for forming an insulating layer for forming a conductor layer) for forming a conductor layer (including a rewiring layer) on the insulating layer.
In particular, from the viewpoint of effectively utilizing the advantage of "a via hole which can suppress the halo phenomenon and can be formed in a good shape", the aforementioned resin composition layer is suitable as: a resin composition layer for forming an insulating layer having a through hole (a resin composition layer for forming an insulating layer having a through hole), among which is particularly suitable as: a resin composition layer for forming an insulating layer having a through hole with a top diameter of 35 μm or less.
[12. Resin sheet ]
The resin sheet of the present invention comprises a support and the resin composition layer of the present invention provided on the support.
Examples of the support include a film made of a plastic material, a metal foil, and a release paper, and a film made of a plastic material and a metal foil are preferable.
When a film made of a plastic material is used as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter, abbreviated as "PET"), polyethylene naphthalate (hereinafter, abbreviated as "PEN"), acrylic polymers such as polycarbonate (hereinafter, abbreviated as "PC"), polymethyl methacrylate (hereinafter, abbreviated as "PMMA"), cyclic polyolefin, triacetyl cellulose (hereinafter, abbreviated as "TAC"), polyether sulfide (hereinafter, abbreviated as "PES"), polyetherketone, polyimide, and the like. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.
When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil, and copper foil is preferable. As the copper foil, a foil formed of copper as a single metal may be used, or a foil formed of an alloy of copper with other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.
The surface of the support to be bonded to the resin composition layer may be subjected to a treatment such as a matting treatment, a corona treatment, or an antistatic treatment.
As the support, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer can be used. Examples of the release agent used for the release layer of the support having a release layer include 1 or more release agents selected from alkyd resins, polyolefin resins, polyurethane resins, and silicone resins. As the support having a release layer, commercially available ones can be used, and examples thereof include PET films having a release layer containing an alkyd-based release agent as a main component, namely, "SK-1", "AL-5", "AL-7" manufactured by Leideaceae; "Lu Miller T60" manufactured by Toli corporation; "Purex" manufactured by Diman corporation; "UNIPEL" manufactured by UNITKA Co., ltd; etc.
The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. When a support with a release layer is used, the thickness of the entire support with a release layer is preferably in the above range.
The resin sheet may contain any layer other than the support and the resin composition layer as required. Examples of the optional layer include a support-based protective film provided on a surface of the resin composition layer not bonded to the support (i.e., a surface opposite to the support). The thickness of the protective film is not particularly limited, and is, for example, 1 μm to 40 μm. The protective film prevents the surface of the resin composition layer from being stained or the like or from being scratched.
The resin sheet can be produced, for example, by: a resin varnish containing an organic solvent and a resin composition is prepared, and the resin varnish is applied to a support by using a coater such as a die coater, and then dried to form a resin composition layer.
Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; acetate solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; a carbitol solvent such as cellosolve and butyl carbitol; aromatic hydrocarbon solvents such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone; etc. For the organic solvent, 1 kind may be used alone, or 2 or more kinds may be used in combination.
Drying may be performed by heating, blowing hot air, or the like. The drying conditions are not particularly limited, and the drying is performed so that the content of the organic solvent in the resin composition layer becomes generally 10 mass% or less, preferably 5 mass% or less. Although the boiling point of the organic solvent varies depending on the resin varnish, for example, when a resin varnish containing 30 to 60 mass% of the organic solvent is used, the resin varnish may be dried at 50 to 150 ℃ for 3 to 10 minutes to form a resin composition layer.
The resin sheet may be wound into a roll and stored. When the resin sheet has a protective film, the protective film is usually peeled off for use.
[13. Printed wiring board ]
The printed wiring board of the present invention includes the insulating layer formed of the cured product of the thinner resin composition layer. Further, the insulating layer can suppress a halo phenomenon when forming a via hole, and can form a well-shaped via hole. Therefore, by using the resin composition layer of the present invention, it is possible to reduce the thickness of the printed wiring board while suppressing degradation of performance due to a halo phenomenon or degradation of the shape of the via hole.
In general, the through hole is provided in order to conduct a conductor layer provided on both sides of an insulating layer having the through hole. Accordingly, the printed wiring board of the present invention generally 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 conducted through the via hole.
By using the advantage of the resin composition layer that "a halo phenomenon can be suppressed and a well-shaped through hole can be formed", a specific printed wiring board which has been difficult to realize in the past can be realized. The specific printed wiring board is a printed wiring board comprising a first conductor layer, a second conductor layer, and an insulating layer formed between the first conductor layer and the second conductor layer, and satisfies all of the following requirements (i) to (v),
(i) The thickness of the insulating layer is below 15 mu m;
(ii) The insulating layer has a through hole with a top diameter of 35 μm or less;
(iii) The taper ratio of the through hole is more than 80%;
(iv) The halo distance of the through hole from the edge of the bottom of the through hole is below 5 μm;
(v) The halo ratio of the via hole with respect to the bottom radius is 35% or less.
The drawings are shown below, and a specific printed wiring board will be described. Fig. 4 is a schematic cross-sectional view of a printed wiring board 300 according to a second embodiment of the present invention. Fig. 4 shows a cross section of the printed wiring board 300 cut off in a plane parallel to the thickness direction of the insulating layer 100 through the center 120C of the via bottom 120 of the via hole 110. In fig. 4, the same reference numerals as those used in fig. 1 to 3 are attached to the parts corresponding to the elements shown in fig. 1 to 3.
As shown in fig. 4, a specific printed wiring board 300 of the second embodiment of the present invention includes: the first conductor layer 210, the second conductor layer 220, and the insulating layer 100 formed between the first conductor layer 210 and the second conductor layer 220. A via hole 110 is formed on the insulating layer 100. In addition, the second conductor layer 220 is typically a layer provided after the formation of the via hole 110. Therefore, the second conductor layer 220 is generally formed not only on the surface 100U of the insulating layer 100 but also in the through hole 110, and the first conductor layer 210 and the second conductor layer 220 are electrically connected through the through hole 110.
The thickness T of the insulating layer 100 included in the specific printed wiring board 300 is usually 15 μm or less, preferably 12 μm or less, more preferably 10 μm or less, and particularly preferably 5 μm or less. Since the specific printed wiring board 300 has the thin insulating layer 100, the specific printed wiring board 300 itself can be thinned. The lower limit of the thickness T of the insulating layer 100 is preferably 1 μm or more, more preferably 2 μm or more, and particularly preferably 3 μm or more from the viewpoint of improving the insulating performance of the insulating layer 100. Here, the thickness T of the insulating layer 100 indicates the size of the insulating layer 100 between the first conductor layer 210 and the second conductor layer 220, and does not indicate the size of the insulating layer 100 at the position where the first conductor layer 210 or the second conductor layer 220 is not present. The thickness T of the insulating layer 100 is generally equal to the distance between the main surface 210U of the first conductor layer 210 and the main surface 220D of the second conductor layer 220, which are opposed to each other with the insulating layer 100 interposed therebetween, and is also equal to the depth of the through hole 110.
The top diameter Lt of the through hole 110 of the insulating layer 100 included in the specific printed wiring board 300 is usually 35 μm or less, preferably 33 μm or less, and particularly preferably 32 μm or less. Since the specific printed wiring board 300 includes the insulating layer 100 having the via hole 110 having the smaller top diameter Lt, miniaturization of the wiring including the first conductor layer 210 and the second conductor layer 220 can be promoted. The lower limit of the top diameter Lt of the through hole 110 is preferably 3 μm or more, more preferably 10 μm or more, particularly preferably 15 μm or more, from the viewpoint of easy formation of the through hole 110.
The taper ratio Lb/Lt (%) of the through hole 110 of the insulating layer 100 included in the specific printed wiring board 300 is generally 80% to 100%. The specific printed wiring board 300 includes the insulating layer 100 having the above-described well-shaped through-holes 110 having a high taper ratio Lb/Lt. Accordingly, the specific printed wiring board 300 can generally improve the reliability of conduction between the first conductor layer 210 and the second conductor layer 220.
The insulating layer 100 included in the specific printed wiring board 300 has a halo distance Wb of the via hole 110 from the edge 170 of the via bottom 120 of usually 5 μm or less, preferably 4 μm or less. For the specific printed wiring board 300, the halo distance Wb from the edge 170 of the via bottom 120 is the above-described small value, and thus the peeling of the insulating layer 100 from the first conductor layer 210 is small. Accordingly, the specific printed wiring board 300 can generally improve the reliability of conduction between the first conductor layer 210 and the second conductor layer 220.
The halo ratio Hb of the through hole 110 of the insulating layer 100 included in the specific printed wiring board 300 to the bottom radius Lb/2 is usually 35% or less, preferably 33% or less, and more preferably 31% or less. For the specific printed wiring board 300, the halo ratio Hb with respect to the bottom radius Lb/2 is the above-described small value, and thus the peeling of the insulating layer 100 from the first conductor layer 210 is small. The particular printed wiring board 300 including the insulating layer 100 having the above-described halo smaller than Hb can generally improve the reliability of conduction between the first conductor layer 210 and the second conductor layer 220. The lower limit of the halo ratio Hb with respect to the bottom radius Lb/2 is desirably zero, but is usually 5% or more.
The number of through holes 110 in the insulating layer 100 included in the specific printed wiring board 300 may be 1 or 2 or more. When the insulating layer 100 has 2 or more through holes 110, some of them may satisfy the requirements (ii) to (v), but it is preferable that all of them satisfy the requirements (ii) to (v). It is also preferable that, for example, the 5 through holes 110 randomly selected from the insulating layer 100 satisfy the requirements (ii) to (v) on average.
The insulating layer 100 is formed by using the cured product of the resin composition layer of the present invention, whereby the specific printed wiring board 300 described above can be realized. In this case, the planar shapes of the via bottom 120 and the via top 130 of the via 110 formed on the insulating layer 100 are arbitrary, but are generally circular or elliptical, and preferably circular.
A printed wiring board such as a specific printed wiring board can be manufactured, for example, as follows: a method for producing a resin sheet, comprising the following steps (I) to (III),
(I) Laminating a resin sheet on the inner substrate so that the resin composition layer and the inner substrate are bonded;
(II) a step of forming an insulating layer by thermally curing the resin composition layer;
(III) a step of forming a via hole in the insulating layer.
The "inner 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. In general, as the inner layer substrate, an inner layer substrate having a conductor layer on one side or both sides thereof is used. Then, an insulating layer is formed over the conductor layer. The conductor layer may be patterned, for example, to function as a circuit. An inner layer substrate having a conductor layer formed as a circuit on one or both sides of the substrate is sometimes referred to as an "inner layer circuit substrate". In addition, in the production of a printed wiring board, intermediate products to be further formed with an insulating layer and/or a conductor layer are also included in the "inner layer substrate". When the printed wiring board is a component-embedded circuit board, an inner layer board having a component embedded therein may be used.
The lamination of the inner layer substrate and the resin sheet can be performed, for example, as follows: the resin sheet is heat-pressed against the inner substrate from the support side, whereby the resin composition layer is bonded to the inner substrate. As a member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter, sometimes referred to as a "thermocompression bonding member"), for example, a heated metal plate (SUS end plate (lens plate) or the like), a metal roller (SUS roller) or the like can be cited. It is preferable that the pressure-applying member is not directly pressed against the resin sheet, but is pressed with an elastic material such as heat-resistant rubber interposed therebetween so that the resin sheet sufficiently follows the surface irregularities of the inner layer substrate.
Lamination of the inner layer substrate and the resin sheet can be performed by, for example, vacuum lamination. In the vacuum lamination method, the heat press-bonding temperature is preferably in the range of 60 ℃ to 160 ℃, more preferably 80 ℃ to 140 ℃, the heat press-bonding pressure is preferably in the range of 0.098mpa to 1.77mpa, more preferably 0.29mpa to 1.47mpa, and the heat press-bonding time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. The lamination is preferably carried out under reduced pressure of 26.7hPa or less.
Lamination can be performed using commercially available vacuum laminators. Examples of commercially available vacuum laminators include: vacuum laminator manufactured by Ming machine Co., ltd., vacuum applicator (vacuum applicator) manufactured by Nikko-Materials Co., ltd.), batch vacuum laminator, etc.
After lamination, the laminated resin sheet may be smoothed by pressurizing the thermocompression bonding member from the support body side at normal pressure (atmospheric pressure), for example. The pressurizing conditions for the smoothing treatment may be set to the same conditions as the above-described heat press bonding conditions for the laminate. The smoothing treatment can be performed by a commercially available laminator. The lamination and smoothing treatment may be continuously performed using the commercially available vacuum laminator described above.
In the step (II), the resin composition layer is thermally cured to form an insulating layer. The heat curing condition of the resin composition layer is not particularly limited, and any condition used in forming an insulating layer of a printed wiring board can be used.
For example, the heat curing condition of the resin composition layer varies depending on the kind of the resin composition, etc., and the curing temperature may be generally in the range of 120 to 240 ℃ (preferably 150 to 220 ℃, more preferably 170 to 200 ℃), and the curing time may be generally in the range of 5 to 120 minutes (preferably 10 to 100 minutes, more preferably 15 to 90 minutes).
The resin composition layer may be preheated at a temperature lower than the curing temperature before the resin composition layer is thermally cured. For example, before the resin composition layer is thermally cured, the resin composition layer is preheated for usually 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, still more preferably 15 minutes to 100 minutes) at a temperature of usually 50 ℃ or more and less than 120 ℃ (preferably 60 ℃ or more and 115 ℃ or less, more preferably 70 ℃ or more and 110 ℃ or less).
In step (III), a via hole is formed in the insulating layer. Examples of the method for forming the through-hole include laser irradiation, etching, and mechanical drilling. Among them, laser irradiation is generally prone to a halo phenomenon. Therefore, laser irradiation is preferable from the viewpoint of effectively utilizing the effect of suppressing the halo phenomenon.
The laser irradiation may be performed using, for example, a laser processing machine having a laser light source such as a carbon dioxide laser, a YAG laser, or an excimer laser. Examples of usable laser beam processors include CO manufactured by Via mechanical Co., ltd 2 Laser beam machines "LC-2k212/2C", 605GTWIII (-P) manufactured by Mitsubishi motor company, and laser beam machines manufactured by Panasonic Welding Systems company.
The irradiation conditions of the laser light such as the wavelength, pulse number, pulse width, output power, etc. of the laser light are not particularly limited, and may be set to appropriate conditions according to the type of the laser light source.
However, the support may be removed between the step (I) and the step (II), between the step (II) and the step (III), or after the step (III). Among them, from the viewpoint of further suppressing the occurrence of the recess, it is preferable to remove the recess after the step (III) of forming the through hole in the insulating layer. For example, if the support is peeled off after forming the through-hole on the insulating layer by laser irradiation, a well-shaped through-hole is easily formed.
The method for manufacturing a printed wiring board may further Include (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer. These steps (IV) and (V) can be performed according to various methods used in the production of printed wiring boards. In the case where the support is removed after the step (III), the removal of the support may be performed between the step (III) and the step (IV) or between the step (IV) and the step (V).
The step (IV) is a step of roughening the insulating layer. The step and condition of the roughening treatment are not particularly limited, and any step and condition used in forming an insulating layer of a printed wiring board can be employed. For example, the insulating layer may be roughened by sequentially performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid.
The swelling liquid is not particularly limited, and examples thereof include an alkali solution, a surfactant solution, and the like, and an alkali solution is preferable. As the alkali solution, sodium hydroxide solution and potassium hydroxide solution are more preferable. Examples of commercially available swelling liquids include "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by ATOTECH JAPAN corporation. In addition, 1 kind of swelling liquid may be used alone, or 2 or more kinds may be used in combination in any ratio. The swelling treatment with the swelling solution is not particularly limited, and for example, the insulating layer may be immersed in the swelling solution at 30 to 90 ℃ for 1 to 20 minutes. From the viewpoint of controlling the swelling of the resin of the insulating layer to a proper level, it is preferable to impregnate the insulating layer in a swelling liquid at 40 to 80 ℃ for 5 to 15 minutes.
The oxidizing agent is not particularly limited, and examples thereof include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. In addition, 1 kind of oxidizing agent may be used alone, or 2 or more kinds may be used in combination in any ratio. Roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60 to 80 ℃ for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5 to 10 mass%. Examples of the commercially available oxidizing agent include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing solution Securiganth P" manufactured by ATOTECH JAPAN corporation.
The neutralizing solution is preferably an acidic aqueous solution, and examples of the commercial product include "Reduction Solution Securiganth P" manufactured by ATOTECH JAPAN corporation. The neutralizing solution may be used alone or in combination of at least 2 kinds in any ratio. The treatment with the neutralizing solution is performed by immersing the treated surface, on which the roughening treatment with the oxidizing agent has been completed, in the neutralizing solution at 30 to 80 ℃ for 5 to 30 minutes. In view of handling properties, it is preferable to impregnate the object subjected to roughening treatment with the oxidizing agent in a neutralizing solution at 40 to 70 ℃ for 5 to 20 minutes.
The step (V) is a step of forming a conductor layer. The conductor material used for the conductor layer is not particularly limited. In a suitable embodiment, the conductor layer comprises a metal selected from 1 or more 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 2 or more metals selected from the above metals (for example, a nickel-chromium alloy, a copper-nickel alloy, and a copper-titanium alloy). Among them, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper is preferable from the viewpoints of versatility of conductor layer formation, cost, ease of pattern formation, and the like; or an alloy layer of nickel-chromium alloy, copper-nickel alloy, copper-titanium alloy. More preferably a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper; or an alloy layer of a nickel-chromium alloy; particularly preferred is a single metal layer of copper.
The conductor layer may have a single-layer structure or a multilayer structure in which 2 or more kinds of single-metal layers or alloy layers made of different kinds of metals or alloys are stacked. When the conductor layer has a multilayer structure, the layer to be connected to the insulating layer is preferably a single metal layer of chromium, zinc or titanium or an alloy layer of nickel-chromium alloy.
The thickness of the conductor layer depends on the design of the desired printed wiring board, but is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.
The conductor layer may be formed using 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 half-addition method or a full-addition method. Among them, the semi-additive method is preferable from the viewpoint of ease of production.
An example of forming the conductor layer by the semi-additive method is shown below. First, a plating seed layer (i.e., a metal っ k) is formed on the surface of an insulating layer by electroless plating (electroless plating). Next, a mask pattern is formed on the formed plating seed layer so as to expose a part of the plating seed layer in correspondence with the desired wiring pattern. After forming a metal layer on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. Then, the unnecessary plating seed layer may be removed by etching or the like to form a conductor layer having a desired wiring pattern.
The steps of forming the insulating layer and the conductor layer in the steps (I) to (V) may be repeated as necessary to produce a multilayer printed wiring board.
[14. Semiconductor device ]
The semiconductor device of the present invention includes the printed wiring board. The semiconductor device may be manufactured using a printed wiring board.
Examples of the semiconductor device include various semiconductor devices used in electric products (for example, computers, mobile phones, digital cameras, televisions, and the like) and vehicles (for example, motorcycles, automobiles, electric trains, ships, aircraft, and the like).
For example, a semiconductor device can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. The "conductive portion" refers to a "portion that conducts an electrical signal in a printed wiring board," and the position thereof may be any of a surface or a buried portion. In addition, the semiconductor chip can arbitrarily use an electric circuit element using a semiconductor as a material.
The mounting method of the semiconductor chip in manufacturing the semiconductor device is not particularly limited as long as the semiconductor chip is effectively functioning, and examples of the mounting method include a wire bonding mounting method, a flip chip mounting method, a mounting method using a solderless build-up layer (BBUL), a mounting method using an Anisotropic Conductive Film (ACF), a mounting method using a non-conductive film (NCF), and the like. Here, the "mounting method using a solderless build-up layer (BBUL)" refers to "a mounting method in which a semiconductor chip is directly buried in a recess of a printed wiring board, and the semiconductor chip is connected to wiring on the printed wiring board".
Examples (example)
Hereinafter, the present invention will be specifically described with reference to examples. The present invention is not limited to the following examples. In the following description, unless otherwise indicated, "part" and "%" representing amounts refer to "part by mass" and "% by mass", respectively. The operations described below are performed under normal temperature and normal pressure conditions unless otherwise specified.
[ description of inorganic filler ]
Method for measuring average particle diameter of inorganic filler
100mg of an inorganic filler, 0.1g of a dispersant (SN 9228 made by Sannopco Co., ltd.) and 10g of methyl ethyl ketone were weighed into a vial, and dispersed by ultrasonic waves for 20 minutes. The particle size distribution of the inorganic filler was measured by a batch cell method using a laser diffraction particle size distribution measuring apparatus (SALD-2200, manufactured by Shimadzu corporation) on a volume basis. Then, from the obtained particle size distribution, the average particle size of the inorganic filler was calculated as the median particle size.
Method for measuring specific surface area of inorganic filler
The specific surface area of the inorganic filler was measured using a BET fully automatic specific surface area measuring apparatus (Macsorb HM-1210, manufactured by mountain Co.).
< kind of inorganic filler >
Inorganic filler 1: spherical silica (UFP-30 manufactured by electric chemical industry Co., ltd., average particle diameter of 0.078 μm, specific surface area of 30.7 m) 2 100 parts by weight of the above-mentioned composition (g) was subjected to a surface treatment with 2 parts by weight of N-phenyl-3-aminopropyl trimethoxysilane (KBM 573, manufactured by Xinyue chemical industry Co., ltd.);
inorganic filler 2: for spherical silica (manufactured by Admatechs Co., ltd. "SC2500SQ", average particle diameter 0.77 μm, specific surface area 5.9 m) 2 100 parts by weight of the resulting composition was surface-treated with 1 part by weight of N-phenyl-3-aminopropyl trimethoxysilane (KBM 573, manufactured by Xinyue chemical industries Co., ltd.).
Example 1 preparation of resin composition 1
While stirring, 6 parts of a bisxylenol type epoxy resin (YX 4000HK, manufactured by Mitsubishi chemical corporation, about 185 in epoxy equivalent), 5 parts of a naphthalene type epoxy resin (ESN 475V, manufactured by Mitsubishi chemical corporation, about 332 in epoxy equivalent), 15 parts of a bisphenol AF type epoxy resin (YL 7760, manufactured by Mitsubishi chemical corporation, about 238 in epoxy equivalent), 2 parts of a cyclohexane type epoxy resin (ZX 1658GS, manufactured by Mitsubishi chemical corporation, about 135 in epoxy equivalent), and 2 parts of a phenoxy resin (YX 7553BH30, manufactured by Mitsubishi chemical corporation, 1:1 solution of cyclohexanone: methyl Ethyl Ketone (MEK), with a nonvolatile content of 30% by mass, mw=35000) were heated and dissolved in a mixed solvent of 20 parts of a solvent naphtha and 10 parts of cyclohexanone. The resulting solution was cooled to room temperature. Then, 5 parts of a naphthol-based curing agent (aromatic hydrocarbon resin represented by formula (5): SN395, available from Nippon Temmine chemical Co., ltd., hydroxyl equivalent weight 107), 6 parts of an active ester-based curing agent (EXB-8000L-65 TM, available from DIC Co., ltd., active group equivalent weight of about 220, a 1:1 solution of toluene, which is not volatile and contains 65% by mass of MEK), 1 part of an inorganic filler (50 parts), and 0.05 part of an amine-based curing accelerator (4-Dimethylaminopyridine (DMAP)) were mixed into the solution, and uniformly dispersed by a high-speed rotary mixer to obtain a mixture. The mixture was filtered through a cartridge filter (SHP 020 manufactured by ROKITECHNO Co., ltd.) to obtain a resin composition 1.
EXAMPLE 2 preparation of resin composition 2
Resin composition 2 was prepared in the same manner as in example 1, except that the types and amounts of the reagents used were changed as shown in table 1. Specific modification points from example 1 are as follows,
instead of 2 parts of cyclohexane type epoxy resin (ZX 1658GS, about 135 epoxy equivalent, manufactured by Mitsubishi chemical corporation), 4 parts of bisphenol type epoxy resin (ZX 1059, about 169 epoxy equivalent, 1:1 mixture of bisphenol A type and bisphenol F type, manufactured by Nippon Kagaku Co., ltd.) and 2 parts of naphthylene ether type epoxy resin (EXA-7311-G4, about 213 epoxy equivalent) were used;
in addition, 2 parts of phenoxy resin (product of Mitsubishi chemical corporation, "YL7500BH30", 1:1 solution of non-volatile component 30% by mass of cyclohexanone: methyl Ethyl Ketone (MEK), mw=44000) was used instead of 2 parts of phenoxy resin (product of Mitsubishi chemical corporation, "YX7553BH30", 1:1 solution of non-volatile component 30% by mass of cyclohexanone: methyl Ethyl Ketone (MEK), mw=35000);
further, as the component (B), 4 parts of a phenol-based curing agent (aromatic hydrocarbon resin represented by the formula (4): GRA13H, manufactured by Kunlun chemical industry Co., ltd., hydroxyl equivalent weight of about 75) was used instead of 5 parts of a naphthol-based curing agent (SN 395, manufactured by Nippon iron gold chemical Co., ltd., hydroxyl equivalent weight of 107).
Comparative example 1 preparation of resin composition 3
Resin composition 3 was prepared in the same manner as in example 1, except that the types and amounts of the reagents used were changed as shown in table 1. Specific modification points from example 1 are as follows,
instead of 2 parts of cyclohexane type epoxy resin (ZX 1658GS, about 135 epoxy equivalent, manufactured by Mitsubishi chemical corporation), 4 parts of bisphenol type epoxy resin (ZX 1059, about 169 epoxy equivalent, 1:1 mixture of bisphenol A type and bisphenol F type, manufactured by Nippon Kagaku Co., ltd.) and 2 parts of naphthylene ether type epoxy resin (EXA-7311-G4, about 213 epoxy equivalent) were used;
in addition, 2 parts of phenoxy resin (product of Mitsubishi chemical corporation, "YL7500BH30", 1:1 solution of non-volatile component 30% by mass of cyclohexanone: methyl Ethyl Ketone (MEK), mw=44000) was used instead of 2 parts of phenoxy resin (product of Mitsubishi chemical corporation, "YX7553BH30", 1:1 solution of non-volatile component 30% by mass of cyclohexanone: methyl Ethyl Ketone (MEK), mw=35000);
further, instead of 5 parts of the naphthol-based curing agent (SN 395, hydroxyl equivalent 107, manufactured by Nippon iron and gold chemical Co., ltd.) 10 parts of a cresyl phenol-type curing agent containing a triazine skeleton (LA-3018-50P, manufactured by DIC Co., ltd., "hydroxyl equivalent 151, a 2-methoxypropanol solution having a nonvolatile content of 50%) was used as the component (E).
Comparative example 2 preparation of resin composition 4
Resin composition 4 was prepared in the same manner as in example 1, except that the types and amounts of the reagents used were changed as shown in table 1. Specific modification points from example 1 are as follows,
4 parts of a cresols-phenolic curing agent containing a triazine skeleton (LA-3018-50P, manufactured by DIC Co., ltd., "LA-3018-50P", a 2-methoxypropanol solution having a hydroxyl equivalent of about 151 and a nonvolatile content of 50%) was used as the component (E) instead of 5 parts of a naphthols-phenolic curing agent (SN 395, manufactured by Nippon iron gold chemical Co., ltd., "hydroxyl equivalent of 107);
further, instead of using the inorganic filler 1 (50 parts), the inorganic filler 2 (80 parts) was used.
Comparative example 3 preparation of resin composition 5
Resin composition 5 was prepared in the same manner as in example 1, except that the types and amounts of the reagents used were changed as shown in table 1. Specific modification points from example 1 are as follows,
4 parts of a naphthol-based curing agent (SN 485, available from Nippon iron and gold chemical Co., ltd., hydroxyl equivalent weight of about 215) and 4 parts of a cresol-phenolic curing agent containing a triazine skeleton (LA-3018-50P, available from DIC Co., ltd., hydroxyl equivalent weight of about 151, a 2-methoxypropanol solution having a nonvolatile content of 50%) were used as the component (E), instead of 5 parts of a naphthol-based curing agent (SN 395, available from Nippon iron and gold chemical Co., ltd., hydroxyl equivalent weight of 107).
Comparative example 4 preparation of resin composition 6
Resin composition 6 was prepared in the same manner as in example 1, except that the types and amounts of the reagents used were changed as shown in table 1. Specific modification points from example 1 are as follows,
as the curing agent, 4 parts of a cresol novolac curing agent containing a triazine skeleton (DIC, "LA-3018-50P", by DIC, a 2-methoxypropanol solution having a hydroxyl equivalent of about 151 and a nonvolatile content of 50%) as the component (E) was used in combination with 5 parts of a naphthol curing agent (SN 395, by Nippon Kagaku Co., ltd., hydroxyl equivalent of 107) and 6 parts of an active ester curing agent (EXB-8000L-65 TM, by DIC, a 1:1 solution of toluene having an active group equivalent of about 220 and a nonvolatile content of 65% by mass of MEK).
In addition, the inorganic filler 2 (80 parts) was used instead of the inorganic filler 1 (50 parts).
[ composition of resin composition ]
The components used in the preparation of the resin compositions 1 to 6 and the amounts thereof (parts by mass of nonvolatile matter) are shown in the following table 1. The abbreviations in the following tables are as follows;
content of curing agent: a content of the curing agent of 100 mass% relative to the resin component in the resin composition;
Content of active ester-based curing agent: the content of the active ester-based curing agent relative to 100 mass% of the resin component in the resin composition;
content of inorganic filler: the content of the inorganic filler is 100% by mass relative to the nonvolatile component in the resin composition.
TABLE 1
Figure 730182DEST_PATH_IMAGE011
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[ production of resin sheet ]
As a support, a polyethylene terephthalate film (Miller R80, manufactured by Toli Co., ltd., thickness: 38 μm, softening point: 130 ℃ C.) having been subjected to a mold release treatment with an alkyd resin-based mold release agent (manufactured by Leidenectar Co., ltd. "AL-5") was prepared.
Resin compositions 1 to 6 were uniformly coated on a support using a die coater, respectively, so that the thickness of the dried resin composition layer was 10. Mu.m, and dried at 70 to 95℃for 2 minutes, thereby forming a resin composition layer on the support. Next, a rough surface of a polypropylene film (ALPHAN MA-411, manufactured by Oji F-Tex Co., ltd., thickness of 15 μm) as a protective film was bonded to the surface of the resin composition layer which was 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.
[ method for measuring thickness ]
The thickness of the layer such as the resin composition layer was measured using a contact film thickness meter (Mitutoyo Co., ltd. "MCD-25 MJ").
[ evaluation of through-holes after laser hole Forming ]
Using the resin sheets a produced from the resin compositions 1 to 6, an insulating layer having a through hole was formed according to the following method, and the through hole was evaluated.
< preparation of sample for evaluation >
(1) Preparation of an inner layer substrate:
as an inner layer substrate, a glass cloth base material epoxy resin double-sided copper-clad laminate (thickness of copper foil 3 μm, substrate thickness 0.15mm, mitsubishi gas chemical corporation "HL832NSF LCA", 255×340mm size) having copper foil layers on both sides was prepared.
(2) Lamination of resin sheets:
the protective film was peeled off from the resin sheet a to expose the resin composition layer. A batch vacuum press laminator (CVP 700 "of 2-stage lamination laminator (2-stage buildup laminator) manufactured by Nikko-Materials Co.) was used to laminate the resin composition layer to the inner substrate on both sides of the inner substrate. Lamination is performed as follows: after the pressure was reduced to 13hPa or less for 30 seconds, the mixture was pressure-bonded at 130℃under a pressure of 0.74MPa for 45 seconds. Then, hot pressing was performed at 120℃under a pressure of 0.5MPa for 75 seconds.
(3) Heat curing of the resin composition layer:
then, the inner substrate laminated with the resin sheet was put into an oven at 100 ℃ and heated for 30 minutes, and then moved to an oven at 180 ℃ and heated for 30 minutes, and the resin composition layer was thermally cured 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 pore-forming processing:
using CO 2 A laser beam machine (Mitsubishi Motor Co., ltd. "605GTWIII (-P)") irradiates the insulating layer with laser beam through the support, and forms a plurality of through holes having a top diameter (diameter) of about 30 μm in the insulating layer. The irradiation conditions of the laser were a mask diameter of 1mm, a pulse width of 16. Mu.s, an energy of 0.2 mJ/shot, a shot count of 2, and a burst mode (10 kHz).
(5) Roughening treatment:
after forming a through hole in the insulating layer, the support is peeled off to obtain a hole-forming processed substrate a having the insulating layer, the inner substrate, and the insulating layer in this order. Then, the hole-formed substrate a is subjected to desmear (desmear) treatment as a roughening treatment. As the desmear treatment, the following wet desmear treatment was performed.
(wet clean drilling treatment)
The pore-forming substrate A was immersed in a swelling solution (ATOTECH JAPAN, manufactured by ATOTECH JAPAN, inc. "Swelling Dip Securiganth P", an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60℃for 10 minutes, then immersed in an oxidizing agent solution (ATOTECH JAPAN, manufactured by ATOTECH JAPAN, inc. "Concentrate Compact CP", an aqueous solution of potassium permanganate concentration of about 6% and sodium hydroxide concentration of about 4%) at 80℃for 20 minutes, then immersed in a neutralization solution (ATOTECH JAPAN, manufactured by ATOTECH JAPAN, inc. "Reduction Solution Securiganth P", an aqueous solution of sulfuric acid) at 40℃for 5 minutes, and then dried at 80℃for 15 minutes. The hole-formed substrate a subjected to the wet desmear treatment is referred to as a roughened substrate a.
< determination of size of via hole before roughening treatment)
As a sample, a hole-forming processed substrate a before roughening treatment was prepared. The hole-formed substrate a was subjected to cross-sectional observation using a FIB-SEM composite device (SMI 3050SE, manufactured by SII Nano Technology). In detail, using FIB (focused ion beam), the insulating layer is cut to present a cross section parallel to the thickness direction of the insulating layer and passing through the center of the via bottom of the via. The cross section was observed by SEM (scanning electron microscope), and the top diameter and bottom diameter of the through hole were measured from the observed image.
The foregoing assays were performed on randomly selected 5 through holes. Then, the average of the measured values of the top diameters of the 5 through holes measured was used as the top diameter Lt1 of the through hole of the sample. Further, the average of the measured values of the bottom diameters of the 5 through holes measured was used as the bottom diameter Lb1 of the through hole of the sample.
< determination of size of through hole after roughening >
As a sample, a roughened substrate a was used instead of the hole-forming substrate a. Except for the above, the same operations as the above-described < measurement of the size of the via hole before roughening > were performed, and the top diameter Lt2 and the bottom diameter Lb2 of the via hole after roughening were measured.
< determination of halo distance before roughening treatment >)
The hole-formed substrate A before the roughening treatment was observed with an optical microscope (product of Hirox Co., ltd. "KH 8700"). Specifically, an insulating layer around the through hole was observed from the upper portion of the hole-forming processed substrate a using an optical microscope (CCD). For this observation, the optical microscope was focused on the top of the through-hole. As a result of the observation, a halo portion was seen around the via hole, which was continuous from the edge of the via hole top of the via hole and the insulating layer became a white ring shape. Therefore, the radius r1 of the top of the through hole (corresponding to the inner peripheral radius of the halo portion) and the outer peripheral radius r2 of the halo portion are measured from the observed image, and the difference r2-r1 between the radius r1 and the radius r2 is calculated as the halo distance from the edge of the top of the through hole at the measurement point.
The foregoing assays were performed on randomly selected 5 through holes. Then, the average of the measured values of the halo distances of the 5-point through holes was used as the halo distance Wt of the sample from the edge of the top of the through hole.
< sizing of halo distance after roughening >)
The roughened substrate A was subjected to cross-sectional observation using a FIB-SEM composite apparatus (manufactured by SII Nano Technology company under the heading "SMI3050 SE"). In detail, using FIB (focused ion beam), the insulating layer is cut to present a cross section parallel to the thickness direction of the insulating layer and passing through the center of the via bottom of the via. The cross section was observed by SEM (scanning electron microscope). As a result of the observation, a gap portion was observed which was continuous from the edge of the bottom of the through hole and formed by peeling the insulating layer from the copper foil layer of the inner layer substrate. From the observed image, a distance r3 from the center of the bottom of the through hole to the edge of the bottom of the through hole (corresponding to the inner peripheral radius of the halo portion) and a distance r4 from the center of the bottom of the through hole to the more distal end of the gap portion (corresponding to the outer peripheral radius of the halo portion) are measured, and a difference r4-r3 between the distances r3 and r4 is calculated as the halo distance from the edge of the bottom of the through hole at the measurement point.
The foregoing assays were performed on randomly selected 5 through holes. Then, the average of the measured values of the halo distances of the through holes at 5 positions was used as the halo distance Wb of the sample from the edge of the bottom of the through hole.
Results (results)
The evaluation results of the foregoing examples and comparative examples are shown in table 2 below.
In table 2, the taper ratio represents the ratio "Lb1/Lt1" of the top diameter Lt1 and the bottom diameter Lb1 of the through hole before the roughening treatment. If the taper ratio Lb1/Lt1 is 75% or more, the hole forming workability is judged as "good"; if the taper ratio Lb1/Lt1 is less than 75%, the hole forming workability is judged as "bad".
In table 2, the halo ratio Ht before roughening treatment indicates the ratio "Wt/(Lt 1/2)" of the halo distance Wt from the edge of the via top before roughening treatment to the radius (Lt 1/2) of the via top of the via before roughening treatment. If the halo ratio Ht is 35% or less, the halo evaluation is judged as "good"; if the halo ratio Ht is greater than 35%, the halo evaluation is determined to be "bad".
In table 2, the halo ratio Hb after roughening indicates the ratio "Wb/(Lb 2/2)" of the halo distance Wb from the edge of the via bottom after roughening and the radius (Lb 2/2) of the via bottom of the via after roughening. If the halo ratio Hb is 35% or less, the halo evaluation is judged as "good"; if the halo ratio Hb is greater than 35%, the halo evaluation is judged as "bad".
TABLE 2
Figure 467194DEST_PATH_IMAGE012
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Discussion of the related art
As is clear from table 2, in the examples, the insulating layer was formed using a thinner resin composition layer having a thickness of 10 μm, and a via hole having a large taper ratio was formed in the insulating layer. From the results, it was confirmed that the insulating layer capable of forming a well-shaped through hole even when the thickness was small could be realized by the resin composition layer of the present invention.
Further, as is clear from table 2, in the examples, the insulating layer was formed using a thinner resin composition layer having a thickness of 10 μm, and the halo ratio of the halo portion accompanying the formation of the via hole was small. From the results, it was confirmed that the insulating layer capable of suppressing the halo phenomenon even when the thickness was thin could be realized by the resin composition layer of the present invention.
In particular, the insulating layer having a thickness of 15 μm or less, a top diameter of the via hole of 35 μm or less, a taper ratio of the via hole of 80% or more, a halo distance of the via hole from the bottom edge of 5 μm or less, and a halo ratio of the via hole to the bottom radius of 35% or less, as obtained in the foregoing examples 1 and 2, has not been conventionally realized. Therefore, such an insulating layer has a remarkable technical significance in recent printed wiring boards in which thinning of the insulating layer is expected.
In examples 1 and 2, specific results when the conductor layer was formed on the insulating layer of the roughened substrate a are not shown, but from the results of the above examples, those skilled in the art can clearly understand that the specific printed wiring board satisfying the requirements (i) to (v) can be obtained by forming the conductor layer on the insulating layer of the roughened substrate a.
In examples 1 and 2, the same results as in the above examples were confirmed, although the degree of difference was found in the case where the (D) component to the (F) component were not contained.
[ description of symbols ]
100. Insulating layer
100U surface of insulating layer opposite to conductor layer
110. Through hole
120. Bottom of the through hole
Center of 120C via bottom
130. Top of through hole
140. Halo part
150. Edge of via top of via
160. Edge portion on outer peripheral side of halo portion
170. Edge of via bottom of via
180. Gap part
190. End of the clearance portion on the outer peripheral side
200. Inner layer substrate
210. Conductor layer (first conductor layer)
220. Second conductor layer
300. Printed wiring board
Bottom diameter of Lb through hole
Top diameter of Lt via
Thickness of T insulating layer
Wt halo distance from edge of via top
Wb is a halo distance from the edge of the via bottom.

Claims (24)

1. A resin composition layer having a thickness of 15 [ mu ] m or less and containing a resin composition,
wherein the resin composition comprises: (A) an epoxy resin; (B) An aromatic hydrocarbon resin containing an aromatic ring which is an aromatic ring having 2 or more hydroxyl groups as a single ring or a condensed ring; (C) an inorganic filler having an average particle diameter of 100nm or less; and (E) a curing agent other than the component (B),
(B) The component (A) is represented by the following formula (1) or formula (2),
Figure FDF0000024511820000011
in the formula (1), R 0 Each independently represents a 2-valent hydrocarbon group, and n1 represents an integer of 0 to 6;
Figure FDF0000024511820000012
in the formula (2), R 1 ～R 4 Each independently represents a hydrogen atom or a hydrocarbon group of 1 valence,
the amount of the component (B) is 5 to 30 mass% based on 100 mass% of the epoxy resin (A),
the amount of the component (C) is 50% by mass or more relative to 100% by mass of the nonvolatile component in the resin composition,
(E) The curing agent comprises an active ester-based curing agent,
the amount of the curing agent (E) is 0.1 mass% or more and 12 mass% or less relative to 100 mass% of the resin component in the resin composition.
2. A resin composition layer having a thickness of 15 [ mu ] m or less and containing a resin composition,
wherein the resin composition comprises: (A) an epoxy resin; (B) An aromatic hydrocarbon resin containing an aromatic ring which is an aromatic ring having 2 or more hydroxyl groups as a single ring or a condensed ring; (C) Specific surface area of 15m 2 An inorganic filler material of/g or more; and (E) a curing agent other than the component (B),
(B) The component (A) is represented by the following formula (1) or formula (2),
Figure FDF0000024511820000013
in the formula (1), R 0 Each independently represents a hydrocarbyl group of valence 2, n1 representsAn integer of 0 to 6;
Figure FDF0000024511820000021
in the formula (2), R 1 ～R 4 Each independently represents a hydrogen atom or a hydrocarbon group of 1 valence,
the amount of the component (B) is 5 to 30 mass% based on 100 mass% of the epoxy resin (A),
the amount of the component (C) is 50% by mass or more relative to 100% by mass of the nonvolatile component in the resin composition,
(E) The curing agent comprises an active ester-based curing agent,
the amount of the curing agent (E) is 0.1 mass% or more and 12 mass% or less relative to 100 mass% of the resin component in the resin composition.
3. The resin composition layer according to claim 1 or 2, wherein the component (B) is represented by the following formula (3) or formula (4),
Figure FDF0000024511820000022
in the formula (3), n2 represents an integer of 0 to 6;
Figure FDF0000024511820000023
in the formula (4), R 1 ～R 4 Each independently represents a hydrogen atom or a 1-valent hydrocarbon group.
4. The resin composition layer according to claim 1 or 2, wherein the thickness of the resin composition layer is 12 μm or less.
5. The resin composition layer according to claim 1 or 2, wherein the thickness of the resin composition layer is 1 μm or more.
6. The resin composition layer according to claim 1, wherein the average particle diameter of the component (C) is 80nm or less.
7. The resin composition layer according to claim 1, wherein the average particle diameter of the component (C) is 50nm or more.
8. The resin composition layer according to claim 2, wherein the specific surface area of the component (C) is 30m 2 And/g.
9. The resin composition layer according to claim 2, wherein the specific surface area of the component (C) is 60m 2 And/g or less.
10. The resin composition layer according to claim 1 or 2, wherein the amount of the component (a) is 10 to 90 mass% relative to 100 mass% of the resin component in the resin composition.
11. The resin composition layer according to claim 10, wherein the amount of the component (a) is 30% by mass or more relative to 100% by mass of the resin component in the resin composition.
12. The resin composition layer according to claim 10, wherein the amount of the component (a) is 80 mass% or less with respect to 100 mass% of the resin component in the resin composition.
13. The resin composition layer according to claim 1 or 2, wherein the amount of the component (B) is 5 mass% or more relative to 100 mass% of the resin component in the resin composition.
14. The resin composition layer according to claim 13, wherein the amount of the component (B) is 9 mass% or more relative to 100 mass% of the resin component in the resin composition.
15. The resin composition layer according to claim 13, wherein the amount of the component (B) is 20 mass% or less with respect to 100 mass% of the resin component in the resin composition.
16. The resin composition layer according to claim 1 or 2, wherein the amount of the component (B) is 10 mass% or more relative to 100 mass% of the component (a).
17. The resin composition layer according to claim 1 or 2, wherein the amount of the component (C) is 90 mass% or less relative to 100 mass% of the nonvolatile component in the resin composition.
18. The resin composition layer according to claim 1 or 2, wherein the amount of the component (C) is 75 mass% or less relative to 100 mass% of the nonvolatile component in the resin composition.
19. The resin composition layer according to claim 1 or 2, wherein the resin composition layer is used to form an insulating layer for forming a conductor layer.
20. The resin composition layer according to claim 1 or 2, wherein the resin composition layer is used to form an interlayer insulating layer of a printed wiring board.
21. The resin composition layer according to claim 1 or 2, wherein the resin composition layer is used to form an insulating layer having a through hole with a top diameter of 35 μm or less.
22. A resin sheet comprising:
support body
The resin composition layer according to any one of claims 1 to 21 provided on a support.
23. A printed wiring board comprising an insulating layer formed of the cured product of the resin composition layer according to any one of claims 1 to 21.
24. A semiconductor device comprising the printed wiring board according to claim 23.
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JPH06136341A (en) * 1992-10-22 1994-05-17 Toray Ind Inc Adhesive
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