JP7310852B2 - resin composition - Google Patents

Description

The present invention relates to resin compositions. Furthermore, it relates to a sheet-like substrate, an adhesive film, a printed wiring board, and a semiconductor device containing the resin composition.

As a technique for manufacturing a printed wiring board, a manufacturing method using a build-up method in which insulating layers and conductor layers are alternately stacked on an inner layer circuit board is known. An insulating layer is generally formed by curing a resin composition. For example, Patent Document 1 describes a resin composition characterized by containing (A) a radically polymerizable compound, (B) an epoxy resin, (C) a curing agent, and (D) a roughening component. .

JP 2014-034580 A

Many proposals have been made for epoxy resin compositions suitable for forming insulating layers of inner layer circuit boards, including the resin composition described in Patent Document 1. In recent years, insulating layers with excellent low dielectric loss tangent have been proposed. There is an increasing demand for formable resin compositions. In addition, as electronic devices become smaller and have higher performance, multi-layered build-up layers are used in multilayer printed wiring boards, and miniaturization and high density wiring are required.

In order to achieve further miniaturization and higher density of wiring, a resin composition with good compatibility that provides an insulating layer with low dielectric loss tangent, good plating adhesion and base adhesion, and excellent smear removal properties Things are required, but the current situation is that we have not reached all these requirements.

An object of the present invention is to provide a highly compatible resin composition that provides an insulating layer having a low dielectric loss tangent, good plating adhesion and substrate adhesion, and excellent smear removal properties; a sheet containing the resin composition. an adhesive film containing the resin composition; a printed wiring board comprising an insulating layer formed using the resin composition; and a semiconductor device.

The inventors of the present invention have found that conventional general resin compositions are inferior in smear removability when the dielectric loss tangent is lowered, that is, there is a trade-off relationship between the dielectric loss tangent and the smear removability. The inventors of the present invention have made intensive studies to solve the above problems, and found that the resin composition contains (A) an epoxy resin, (B) a curing agent, and a predetermined amount of (C) a cyclic ether structure having a five-membered ring or more. The present inventors have found that the inclusion of a compound results in an insulating layer having a low dielectric loss tangent, good plating adhesion and substrate adhesion, and excellent smear removal properties, thereby completing the present invention.

［１３］ プリント配線板の絶縁層形成用である、［１］～［１２］のいずれかに記載の樹脂組成物。
［１４］ プリント配線板の層間絶縁層形成用である、［１］～［１２］のいずれかに記載の樹脂組成物。
［１５］ ［１］～［１４］のいずれかに記載の樹脂組成物を含む、シート状基材。
［１６］ 支持体と、該支持体上に設けられた、［１］～［１４］のいずれかに記載の樹脂組成物で形成された樹脂組成物層とを含む、接着フィルム。
［１７］ 第１の導体層、第２の導体層、及び、第１の導体層と第２の導体層との間に形成された絶縁層を含むプリント配線板であって、
該絶縁層は、［１］～［１４］のいずれかに記載の樹脂組成物の硬化物である、プリント配線板。
［１８］ ［１７］に記載のプリント配線板を備える、半導体装置。 That is, the present invention includes the following contents.
[1] A resin composition containing (A) an epoxy resin, (B) a curing agent, and (C) a compound having a 5-membered or more cyclic ether structure,
A resin composition in which the content of component (C) is 1% by mass to 50% by mass when the resin component is taken as 100% by mass.
[2] The resin composition according to [1], wherein the content of component (A) is 5% by mass to 50% by mass based on 100% by mass of the resin component.
[3] The resin composition according to [1] or [2], wherein the content of component (B) is 5% by mass to 60% by mass when the resin component is 100% by mass.
[4] The resin composition according to any one of [1] to [3], wherein component (B) is an active ester curing agent.
[5] The resin composition according to any one of [1] to [4], containing (D) an inorganic filler.
[6] The resin composition according to [5], wherein the content of component (D) is 50% by mass or more based on 100% by mass of non-volatile components in the resin composition.
[7] The resin composition according to any one of [1] to [6], wherein component (C) contains a dioxane structure.
[8] The resin composition according to any one of [1] to [7], wherein component (C) has a carbon-carbon unsaturated bond.
[9] The resin composition according to any one of [1] to [8], wherein component (C) has a carbon-carbon double bond.
[10] Component (C) has one or more functional groups selected from the group consisting of vinyl groups, methacrylic groups, acrylic groups, allyl groups, styryl groups, and propenyl groups [1] to [9] The resin composition according to any one of.
[11] The resin composition according to any one of [1] to [10], wherein component (C) has a vinyl group.
[12] The resin composition according to any one of [1] to [11], wherein component (C) is the following compound.

[13] The resin composition according to any one of [1] to [12], which is for forming an insulating layer of a printed wiring board.
[14] The resin composition according to any one of [1] to [12], which is used for forming an interlayer insulating layer of a printed wiring board.
[15] A sheet-like substrate comprising the resin composition according to any one of [1] to [14].
[16] An adhesive film comprising a support and a resin composition layer provided on the support and formed of the resin composition according to any one of [1] to [14].
[17] 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,
A printed wiring board, wherein the insulating layer is a cured product of the resin composition according to any one of [1] to [14].
[18] A semiconductor device comprising the printed wiring board according to [17].

According to the present invention, a highly compatible resin composition that provides an insulating layer having a low dielectric loss tangent, good plating adhesion and substrate adhesion, and excellent smear removal properties; a sheet containing the resin composition; an adhesive film containing the resin composition; a printed wiring board comprising an insulating layer formed using the resin composition; and a semiconductor device.

FIG. 1 is a partial cross-sectional view schematically showing an example of a printed wiring board.

Hereinafter, the resin composition, sheet-like base material, adhesive film, printed wiring board, and semiconductor device of the present invention will be described in detail.

[Resin composition]
The resin composition of the present invention is a resin composition containing (A) an epoxy resin, (B) a curing agent, and (C) a compound having a 5- or more-membered cyclic ether structure, and containing component (C). The amount is 1% by mass to 50% by mass when the resin component is 100% by mass. As a result, it is possible to provide a highly compatible resin composition that provides an insulating layer having a low dielectric loss tangent, good plating adhesion and substrate adhesion, and excellent smear removal properties.

The term “resin component” refers to non-volatile components constituting the resin composition, excluding (D) an inorganic filler described later. Each component contained in the resin composition will be described in detail below.

<(A) Epoxy resin>
The resin composition contains (A) an epoxy resin. (A) Epoxy resins include, for example, bisphenol AF type epoxy resins and fluorine-containing epoxy resins such as perfluoroalkyl type epoxy resins; bisphenol A type epoxy resins; bisphenol F type epoxy resins; bisphenol S type epoxy resins; type epoxy resin; dicyclopentadiene type epoxy resin; trisphenol type epoxy resin; naphthol novolak type epoxy resin; phenol novolak type epoxy resin; tert-butyl-catechol type epoxy resin; naphthalene type epoxy resin; Epoxy resin; Glycidylamine type epoxy resin; Glycidyl ester type epoxy resin; Cresol novolac type epoxy resin; Biphenyl type epoxy resin; Linear aliphatic epoxy resin; Resins; spiro ring-containing epoxy resins; cyclohexanedimethanol-type epoxy resins; naphthylene ether-type epoxy resins; trimethylol-type epoxy resins; An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type.

The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. When the non-volatile component of the epoxy resin is 100 mass %, at least 50 mass % or more of the epoxy resin preferably has two or more epoxy groups in one molecule. The epoxy resin has two or more epoxy groups in one molecule and is liquid at a temperature of 20°C (hereinafter referred to as "liquid epoxy resin"), and/or three or more epoxy groups in one molecule. and is solid at a temperature of 20° C. (hereinafter referred to as “solid epoxy resin”). As the epoxy resin, a liquid epoxy resin and a solid epoxy resin may be used in combination.

Examples of liquid epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, and an ester skeleton. An alicyclic epoxy resin having a type epoxy resins and naphthalene type epoxy resins are more preferred. Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resins) manufactured by DIC Corporation, and "828US" and "jER828EL" (bisphenol A type epoxy resins) manufactured by Mitsubishi Chemical Corporation. , "jER807" (bisphenol F type epoxy resin), "jER152" (phenol novolac type epoxy resin), "630", "630LSD" (glycidylamine type epoxy resin), Nippon Steel & Sumikin Chemical Co., Ltd. "ZX1059" (bisphenol A type epoxy resin and bisphenol F type epoxy resin), "YD-8125G" (bisphenol A type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., "EX-721" manufactured by Nagase ChemteX Corporation (glycidyl ester type epoxy resin) , Daicel "Celoxide 2021P" (alicyclic epoxy resin having an ester skeleton), "PB-3600" (epoxy resin having a butadiene structure), Nippon Steel Chemical "ZX1658", "ZX1658GS" ( liquid 1,4-glycidylcyclohexane), Mitsubishi Chemical's "630LSD" (glycidylamine type epoxy resin), Daikin Industries Ltd.'s "E-7432", "E-7632" (perfluoroalkyl type epoxy resin), etc. is mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more type.

Solid epoxy resins include naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, Anthracene type epoxy resin, bisphenol A type epoxy resin and tetraphenylethane type epoxy resin are preferred, and naphthalene type tetrafunctional epoxy resin, naphthol type epoxy resin and biphenyl type epoxy resin are more preferred. Specific examples of solid epoxy resins include "HP4032H" (naphthalene-type epoxy resin), "HP-4700", "HP-4710" (naphthalene-type tetrafunctional epoxy resin), "N-690" ( cresol novolak type epoxy resin), "N-695" (cresol novolak type epoxy resin), "HP-7200", "HP-7200HH", "HP-7200H" (dicyclopentadiene type epoxy resin), "EXA-7311 ”, “EXA-7311-G3”, “EXA-7311-G4”, “EXA-7311-G4S”, “HP6000” (naphthylene ether type epoxy resin), “EPPN-502H” manufactured by Nippon Kayaku Co., Ltd. ( Trisphenol type epoxy resin), "NC7000L" (naphthol novolak type epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin), Nippon Steel & Sumikin Chemical Co., Ltd. "ESN475V" ( naphthalene type epoxy resin), "ESN485" (naphthol novolac type epoxy resin), Mitsubishi Chemical Corporation's "YX4000H", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bixylenol type epoxy resin), "YX8800" (anthracene type epoxy resin), Osaka Gas Chemicals Co., Ltd. "PG-100", "CG-500", Mitsubishi Chemical Co., Ltd. "YL7800" (fluorene type epoxy resin), Mitsubishi Chemical Co., Ltd. "jER1010", ( solid bisphenol A type epoxy resin), "jER1031S" (tetraphenylethane type epoxy resin), "YL7760" (bisphenol AF type epoxy resin), and the like.

When a liquid epoxy resin and a solid epoxy resin are used together as the epoxy resin, the ratio by mass (liquid epoxy resin: solid epoxy resin) is in the range of 1:0.1 to 1:15. A range of 1:0.1 to 1:10 is preferred, and a range of 1:0.3 to 1:3 is even more preferred.

From the viewpoint of obtaining an insulating layer exhibiting good tensile breaking strength and insulation reliability, the content of the epoxy resin in the resin composition is preferably 5% by mass or more, more preferably 5% by mass or more, when the resin component is 100% by mass. It is 10% by mass or more, more preferably 20% by mass or more. The upper limit of the content of the epoxy resin is not particularly limited as long as the effect of the present invention is exhibited, but it is preferably 50% by mass or less, more preferably 40% by mass or less.

The epoxy equivalent of the epoxy resin is preferably 50-5000, more preferably 50-3000, even more preferably 80-2000, still more preferably 110-1000. Within this range, the crosslink density of the cured product of the resin composition layer is sufficient, and an insulating layer with a small surface roughness can be obtained. The epoxy equivalent can be measured according to JIS K7236, and is the mass of a resin containing one equivalent of epoxy groups.

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

<(B) Curing agent>
The resin composition contains (B) a curing agent. The curing agent (A) is not particularly limited as long as it has a function of curing the epoxy resin. and carbodiimide-based curing agents. A single curing agent may be used alone, or two or more curing agents may be used in combination. Component (B) is preferably one or more selected from phenol-based curing agents, naphthol-based curing agents, active ester-based curing agents, carbodiimide-based curing agents, and cyanate ester-based curing agents, and lowers the dielectric loss tangent. From the point of view, it is preferably an active ester curing agent.

As the phenolic curing agent and the naphtholic curing agent, a phenolic curing agent having a novolac structure or a naphtholic curing agent having a novolac structure is preferable from the viewpoint of heat resistance and water resistance. From the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenolic curing agent is preferable, and a triazine skeleton-containing phenolic curing agent is more preferable.

Specific examples of phenol-based curing agents and naphthol-based curing agents include "MEH-7700", "MEH-7810" and "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., "NHN" manufactured by Nippon Kayaku Co., Ltd., "CBN", "GPH", Nippon Steel & Sumikin "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V", "SN375", "SN395" , "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500" manufactured by DIC.

The active ester curing agent is not particularly limited, but in general, one molecule of an ester group with high reaction activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, etc. A compound having two or more in it is preferably used. The active ester curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferred. Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, Benzenetriol, dicyclopentadiene-type diphenol compound, phenol novolak, and the like. Here, the term "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

Specifically, an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and an active ester compound containing a benzoylated product of phenol novolak are preferred. Among them, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene-type diphenol structure are more preferable. "Dicyclopentadiene-type diphenol structure" represents a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

Commercially available active ester curing agents include, as active ester compounds containing a dicyclopentadiene type diphenol structure, "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", and "HPC-8000H- 65TM", "EXB-8000L-65TM" (manufactured by DIC), "EXB9416-70BK" (manufactured by DIC) as an active ester compound containing a naphthalene structure, and "DC808" as an active ester compound containing an acetylated phenol novolac ( Mitsubishi Chemical Corporation), "YLH1026" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing a benzoylated phenol novolak, "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester curing agent that is an acetylated phenol novolak, "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.), "YLH1030" (manufactured by Mitsubishi Chemical Co., Ltd.), "YLH1048" (manufactured by Mitsubishi Chemical Co., Ltd.) and the like can be mentioned as active ester curing agents that are benzoylated phenol novolacs.

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

Examples of cyanate ester curing agents include bisphenol A dicyanate, polyphenolcyanate, oligo(3-methylene-1,5-phenylenecyanate), 4,4′-methylenebis(2,6-dimethylphenylcyanate), 4,4 '-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatophenylmethane), bis(4-cyanate-3,5-dimethyl Bifunctional cyanate resins such as phenyl)methane, 1,3-bis(4-cyanatophenyl-1-(methylethylidene))benzene, bis(4-cyanatophenyl)thioether, and bis(4-cyanatophenyl)ether, phenol Polyfunctional cyanate resins derived from novolacs, cresol novolaks, etc., and prepolymers obtained by partially triazine-forming these cyanate resins. Specific examples of cyanate ester curing agents include "PT30" and "PT60" (phenol novolac type polyfunctional cyanate ester resins), "ULL-950S" (polyfunctional cyanate ester resins) and "BA230" manufactured by Lonza Japan. , "BA230S75" (a prepolymer in which part or all of bisphenol A dicyanate is triazined to form a trimer), and the like.

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

The ratio of the epoxy resin to the curing agent is [total number of epoxy groups in the epoxy resin]:[total number of reactive groups in the curing agent], and is preferably in the range of 1:0.01 to 1:3. 1:0.015 to 1:2 is more preferred, and 1:0.02 to 1:1.5 is even more preferred. Here, the reactive group of the curing agent is an active hydroxyl group, an active ester group, or the like, and varies depending on the type of curing agent. In addition, the total number of epoxy groups in the epoxy resin is the sum of the values obtained by dividing the solid content mass of each epoxy resin by the epoxy equivalent for all epoxy resins, and the total number of reactive groups in the curing agent is It is a value obtained by dividing the solid content mass of each curing agent by the reactive group equivalent and totaling all the curing agents. By setting the ratio between the epoxy resin and the curing agent within this range, the heat resistance of the cured product of the resin composition layer is further improved.

The content of the curing agent is not particularly limited, but when the resin component is 100% by mass, it is preferably 60% by mass or less, more preferably 55% by mass or less, and even more preferably 50% by mass or less. The lower limit is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 20% by mass or more. By setting the content of the curing agent to 5% by mass or more, it is possible to improve plating adhesion and substrate adhesion. In addition, when the amount is 60% by mass or less, the smear removability can be improved in the active ester curing agent, and the dielectric loss tangent can be lowered in the phenol curing agent and the naphthol curing agent.

<(C) a compound having a 5-membered or higher cyclic ether structure>
The resin composition contains 1% by mass to 50% by mass of (C) a compound having a 5- or more-membered cyclic ether structure, based on 100% by mass of the resin component.

As described above, the dielectric loss tangent and the smear removal property have conventionally been in a trade-off relationship. In addition, it is possible to improve the smear removability. A cyclic ether having a five- or more-membered ring has a property of low dielectric loss tangent due to restricted movement of molecules. In addition, since cyclic ethers having five or more-membered rings are polar, they are hydrophilic to some extent. Hydrophilicity facilitates smear removal and improves smear removability. Furthermore, it is believed that compatibility, plating adhesion, and substrate adhesion are improved due to the presence of polarity and hydrophilicity. However, the technical scope of the present invention is not limited by the explanation of the mechanism for obtaining the effects described here.

The number of oxygen atoms contained in the cyclic ether structure is preferably 1 or more, more preferably 2 or more, from the viewpoint of significantly obtaining the desired effects of the present invention. Although the lower limit is not particularly limited, it is preferably 5 or less, more preferably 4 or less, and even more preferably 3 or less.

The 5- or more-membered cyclic ether structure is not particularly limited as long as it is a 5-membered or more ring, and may be monocyclic, polycyclic, or condensed. Moreover, the (C) component may have a plurality of cyclic ether structures. The cyclic ether structure is preferably a 5- to 10-membered ring, more preferably a 5- to 8-membered ring, even more preferably a 5- to 6-membered ring. Specific examples of 5- or more-membered cyclic ether structures include a furan structure, a tetrahydrofuran structure, a dioxolane structure, a pyran structure, a dihydropyran structure, a tetrahydropyran structure, and a dioxane structure. , the compound having a 5- or more-membered cyclic ether structure preferably contains a dioxane structure. The dioxane structure is a concept including a 1,2-dioxane structure, a 1,3-dioxane structure and a 1,4-dioxane structure, with the 1,3-dioxane structure being preferred.

Further, a substituent such as an alkyl group or an alkoxy group may be bonded to the 5-membered or more cyclic ether structure. The number of carbon atoms in these substituents is usually 1-6 (preferably 1-3).

Component (C) preferably has a carbon-carbon unsaturated bond, more preferably a carbon-carbon double bond, from the viewpoint of lowering the dielectric loss tangent. The carbon-carbon unsaturated bond may be present within the cyclic ether structure or outside the cyclic ether structure, but is preferably present as a functional group to be described later. A plurality of carbon-carbon unsaturated bonds may be present in component (C).

Component (C) is selected from the group consisting of a vinyl group, a methacrylic group, an acrylic group, an allyl group, a styryl group, and a propenyl group from the viewpoint of lowering the dielectric loss tangent and making it easier to react with the component (A). It preferably has at least one functional group, and more preferably has a vinyl group. The functional group may be present in any component (C) and may be present in the cyclic ether structure or outside the cyclic ether structure. You may have multiple functional groups.

（式（１）中、環Ａは５員環以上の環状エーテル構造を有する２価の基を表し、Ｂ^１及びＢ^２はそれぞれ独立に単結合又は２価の連結基を表し、Ｃ^１及びＣ^２はそれぞれ独立に官能基を表す。） A compound having a 5-membered or more cyclic ether structure is preferably represented by the following general formula (1).

(In formula (1), ring A represents a divalent group having a 5-membered or more cyclic ether structure, B ¹ and B ² each independently represent a single bond or a divalent linking group, C ¹ and Each ^C2 independently represents a functional group.)

Ring A represents a divalent group having a 5- or more-membered cyclic ether structure. The 5-membered or more cyclic ether structure is the same as the 5-membered or more cyclic ether structure described above, and the preferred range is also the same.

Specific examples of divalent groups having a 5-membered or higher cyclic ether structure include furan-2,5-diyl group, tetrahydrofuran-2,5-diyl group, dioxolane-2,5-diyl group, pyran- 2,5-diyl group, dihydropyran-2,5-diyl group, tetrahydropyran-2,5-diyl group, 1,2-dioxane-3,6-diyl group, 1,3-dioxane-2,5- diyl group, 1,4-dioxane-2,5-diyl group, 5-ethyl-1,3-dioxane-2,5-diyl group and the like, and 5-ethyl-1,3-dioxane-2,5 -diyl groups are preferred.

B ¹ and B ² each independently represent a single bond or a divalent linking group, preferably a divalent linking group. Examples of the divalent linking group include an optionally substituted alkylene group, an optionally substituted alkynylene group, an optionally substituted arylene group, and a substituted Heteroarylene group, ester bond, ether bond, amide bond, urea bond, urethane bond, group represented by -C(=O)-, -S-, -SO-, -NH-, etc. and may be a group obtained by combining a plurality of these groups.

The alkylene group which may have a substituent is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, an alkylene group having 1 to 5 carbon atoms, or An alkylene group having 1 to 3 carbon atoms is more preferred. The alkylene group may be linear, branched or cyclic. Examples of such an alkylene group include a methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, 1,1-dimethylethylene group and the like. - dimethylethylene group is preferred.

The alkylene group may have a substituent. The substituents are not particularly limited, and examples thereof include halogen atoms, —OH, —O—C _1-6 alkyl groups, —N(C _1-6 alkyl groups) ₂ , C _1-6 alkyl groups, C _{6- 10} aryl group, —NH ₂ , —CN, —C(O)O—C _1-6 alkyl group, —COOH, —C(O)H, —NO ₂ and the like.

Here, the term “C _p−q ” (where p and q are positive integers and satisfies p<q) means that the organic group described immediately after this term has p to q carbon atoms. represents something. For example, the expression "C _1-6 alkyl group" indicates an alkyl group having from 1 to 6 carbon atoms.

The substituents described above may further have a substituent (hereinafter sometimes referred to as a "secondary substituent"). As secondary substituents, unless otherwise specified, the same substituents as described above may be used.

The alkynylene group which may have a substituent is preferably an alkynylene group having 2 to 10 carbon atoms, more preferably an alkynylene group having 2 to 6 carbon atoms, and further an alkynylene group having 2 to 5 carbon atoms. preferable. Examples of alkynylene groups include ethynylene, propynylene, butynylene, pentynylene, and hexynylene groups. The substituent which the alkynylene group may have is the same as the substituent which the alkylene group may have.

The arylene group which may have a substituent is preferably an arylene group having 6 to 14 carbon atoms, more preferably an arylene group having 6 to 10 carbon atoms. The arylene group includes, for example, a phenylene group, a naphthylene group, an anthracenylene group and the like. The substituent which the arylene group may have is the same as the substituent which the alkylene group may have.

The heteroarylene group which may have a substituent is preferably a heteroarylene group having 3 to 15 carbon atoms, more preferably a heteroarylene group having 3 to 9 carbon atoms, and a heteroarylene group having 3 to 6 carbon atoms. Arylene groups are more preferred. Heteroarylene groups include, for example, a furandiyl group, a pyridinediyl group, a thiophenediyl group, and the like. The substituent which the heteroarylene group may have is the same as the substituent which the alkylene group may have.

Among these, B ¹ and B ² are groups in which one or more selected from an optionally substituted alkylene group, an optionally substituted alkynylene group, an ester bond, and an ether bond are combined. is preferred, and a group obtained by combining one or more selected from optionally substituted alkylene groups and ester bonds is more preferred.

C ¹ and C ² each independently represent a functional group. Examples of the functional group include vinyl group, methacrylic group, acrylic group, allyl group, styryl group, propenyl group, and epoxy group, and vinyl group is more preferable.

Specific examples (exemplary compounds) of the component (C) are shown below, but the component (C) is not limited to these.

As the component (C), commercially available products may be used, for example, Shin-Nakamura Chemical Co., Ltd. "A-DOG" (compound of the above specific example), Nippon Kayaku Co., Ltd. "KAYARAD R-604" (above compounds of specific examples), and the like.

The content of component (C) is 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, when the resin component is 100% by mass. The upper limit is 50% by mass or less, preferably 48% by mass or less, more preferably 45% by mass or less, and even more preferably 40% by mass or less. By making the content 1% by mass or more, the dielectric loss tangent can be lowered and the smear removal property can be improved. can.

The mass ratio of epoxy resin to component (C) (epoxy resin: mass of component (C)) is preferably in the range of 1:0.01 to 1:100, more preferably in the range of 1:0.1 to 1:90. More preferably, the range is from 1:0.1 to 1:80. Compatibility can be improved by making it into such a range.

<(D) Inorganic filler>
The resin composition may contain (D) an inorganic filler in addition to the components (A) to (C) from the viewpoint of lowering the dielectric loss tangent and improving the smear removability.

The material of the inorganic filler is not particularly limited, but examples include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, and water. Aluminum oxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide , zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. As silica, spherical silica is preferable. An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type.

The average particle diameter of the inorganic filler is preferably 3 μm or less, more preferably 2 μm or less, and even more preferably 1 μm or less, from the viewpoints of obtaining an insulating layer with a small surface roughness and improving fine wiring formability. Although the lower limit of the average particle diameter is not particularly limited, it is preferably 0.01 μm or more, more preferably 0.1 μm or more, and still more preferably 0.3 μm or more. Examples of commercially available inorganic fillers having such an average particle size include “YC100C”, “YA050C”, “YA050C-MJE” and “YA010C” manufactured by Admatechs, and “UFP-30” manufactured by Denki Kagaku Kogyo. ”, “Silfil NSS-3N”, “Silfil NSS-4N” and “Silfil NSS-5N” manufactured by Tokuyama, “SO-C2” and “SO-C1” manufactured by Admatechs.

The average particle size of the inorganic filler can be measured by a laser diffraction/scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is prepared on a volume basis using a laser diffraction/scattering particle size distribution analyzer, and the median diameter thereof can be used as the average particle size for measurement. As a measurement sample, an inorganic filler dispersed in methyl ethyl ketone by ultrasonic waves can be preferably used. As the laser diffraction scattering type particle size distribution analyzer, Horiba's "LA-500", Shimadzu Corporation's "SALD-2200" and the like can be used.

From the viewpoint of improving moisture resistance and dispersibility, inorganic fillers include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, and silane coupling agents. It is preferably treated with one or more surface treatment agents such as ring agents, alkoxysilanes, organosilazane compounds and titanate coupling agents, and more preferably treated with a fluorine-containing silane coupling agent. Examples of commercially available surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical Industry Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "SZ-31" ( Hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd. "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM-4803" (long-chain epoxy type silane coupling agent), Shin-Etsu Chemical Co., Ltd. "KBM- 7103” (3,3,3-trifluoropropyltrimethoxysilane).

From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment with the surface treatment agent is 0.2 parts by mass to 5 parts by mass of the surface treatment agent with respect to 100 parts by mass of the inorganic filler. preferably 0.2 to 3 parts by mass, more preferably 0.3 to 2 parts by mass.

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

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

When the resin composition contains an inorganic filler, the content of the inorganic filler reduces the dielectric loss tangent and improves the smear removability. It is preferably 50% by mass or more, more preferably 55% by mass or more, still more preferably 60% by mass or more, 65% by mass or more, or 70% by mass or more. The upper limit of the content of the inorganic filler in the resin composition is preferably 90% by mass or less, more preferably 85% by mass or less, still more preferably 80% by mass or less, or 75% by mass, from the viewpoint of the mechanical strength of the insulating layer. % or less.

<(E) Curing accelerator>
In one embodiment, the resin composition may contain (E) a curing accelerator. Examples of curing accelerators include phosphorus curing accelerators, amine curing accelerators, imidazole curing accelerators, guanidine curing accelerators, metal curing accelerators, organic peroxide curing accelerators, and the like. , phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators are preferable, and imidazole-based curing accelerators and organic peroxide-based curing accelerators are more preferable. A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more type.

Phosphorus curing accelerators include, for example, triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate. , tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate, and triphenylphosphine and tetrabutylphosphonium decanoate are preferred.

Examples of amine curing accelerators 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, and 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene are preferred.

Examples of imidazole curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecyl imidazolyl-(1′)]-ethyl-s-triazine, 2,4-diamino-6-[2′-ethyl-4′-methylimidazolyl-(1′)]-ethyl-s-triazine, 2,4- Diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanurate, 2-phenylimidazole isocyanurate, 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, with 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole being preferred.

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

Guanidine curing accelerators include, for example, 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-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 -allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide and the like, with dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene being preferred.

Metal-based curing accelerators include, for example, organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organocobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organocopper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. and the like, 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 organic metal salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

Organic peroxide curing accelerators include, for example, dicumyl peroxide, cyclohexanone peroxide, tert-butyl peroxybenzoate, methyl ethyl ketone peroxide, dicumyl peroxide, tert-butylcumyl peroxide, di-tert-butyl Peroxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, tert-butyl hydroperoxide and the like. As the organic peroxide-based curing accelerator, a commercially available product may be used, and examples thereof include "Percumyl D" manufactured by NOF Corporation.

When the resin composition contains a curing accelerator, the content of the curing accelerator is preferably 0.01% by mass to 1% by mass when the non-volatile component in the resin composition is 100% by mass, and 0.01 % to 0.5% by mass is more preferred, and 0.01% to 0.1% by mass is even more preferred.

<(F) Indene cumarone resin>
In one embodiment, the resin composition may contain (F) an indene cumarone resin. Examples of the indene cumarone resin include copolymers of indene and coumarone, copolymers of indene, coumarone and styrene, and the like.

The content ratio of the coumarone component in the indene cumarone resin is preferably 5 mol % or more, more preferably 8 mol % or more, still more preferably 10 mol % or more. The upper limit is preferably 40 mol % or less, more preferably 35 mol % or less, still more preferably 30 mol % or less.

The content ratio of the indene component in the indene cumarone resin is preferably 30 mol % or more, more preferably 35 mol % or more, and still more preferably 40 mol % or more. The upper limit is preferably 80 mol % or less, more preferably 75 mol % or less, still more preferably 70 mol % or less.

When the indene cumarone resin is a copolymer of indene, coumarone and styrene, the content of the styrene component is preferably 20 mol % or more, more preferably 25 mol % or more, and even more preferably 30 mol % or more. The upper limit is preferably 70 mol % or less, more preferably 65 mol % or less, still more preferably 60 mol % or less.

Specific examples of the indene cumarone resin include "H-100", "V-120S", "V-120" manufactured by Nichinuri Kagaku Co., Ltd., and the like.

When the resin composition contains an indene cumarone resin, from the viewpoint of improving compatibility, the content of the indene cumarone resin is 0.1 to 3 when the non-volatile component in the resin composition is 100% by mass. % by mass is preferable, 0.3 to 2% by mass is more preferable, and 0.5 to 1.5% by mass is even more preferable.

<(G) Thermoplastic resin>
In one embodiment, the resin composition may contain (G) a thermoplastic resin. Examples of thermoplastic resins include phenoxy resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyimide resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polycarbonate resins, polyether resins. Examples include ether ketone resins and polyester resins, and phenoxy resins are preferred. The thermoplastic resin may be used singly or in combination of two or more.

The polystyrene equivalent weight average molecular weight of the thermoplastic resin is preferably 8,000 or more, more preferably 10,000 or more, even more preferably 20,000 or more, and particularly preferably 40,000 or more. Although the upper limit is not particularly limited, it is preferably 70,000 or less, more preferably 60,000 or less. The polystyrene equivalent weight average molecular weight of the thermoplastic resin is measured by a gel permeation chromatography (GPC) method. Specifically, the polystyrene-equivalent weight average molecular weight of the thermoplastic resin is measured by LC-9A/RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P/K-804L/K- manufactured by Showa Denko Co., Ltd. as a column. 804L can be measured at a column temperature of 40° C. using chloroform or the like as a mobile phase, and can be calculated using a standard polystyrene calibration curve.

Examples of phenoxy resins include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, and terpene. A phenoxy resin having one or more skeletons selected from the group consisting of a skeleton and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. A phenoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type. Specific examples of phenoxy resins include Mitsubishi Chemical's "1256" and "4250" (both phenoxy resins containing bisphenol A skeleton), "YX8100" (phenoxy resin containing bisphenol S skeleton), and "YX6954" (bisphenolacetophenone). skeleton-containing phenoxy resin), and in addition, "FX280" and "FX293" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; ”, “YL6794”, “YL7213”, “YL7290” and “YL7482”.

Examples of polyvinyl acetal resins include polyvinyl formal resins and polyvinyl butyral resins, and polyvinyl butyral resins are preferred. Specific examples of polyvinyl acetal resins include Denka Butyral 4000-2, Denka Butyral 5000-A, Denka Butyral 6000-C, Denka Butyral 6000-EP, and Sekisui. S-lec BH series, BX series (for example, BX-5Z), KS series (for example, KS-1), BL series, BM series manufactured by Kagaku Kogyo Co., Ltd. may be mentioned.

Specific examples of the polyimide resin include "Ricacoat SN20" and "Ricacoat PN20" manufactured by Shin Nippon Rika. Specific examples of polyimide resins also include linear polyimides obtained by reacting bifunctional hydroxyl group-terminated polybutadiene, diisocyanate compounds and tetrabasic acid anhydrides (polyimides described in JP-A-2006-37083), and polysiloxane skeletons. Examples include modified polyimides such as polyimide containing (polyimides described in JP-A-2002-12667 and JP-A-2000-319386).

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

Specific examples of the polyethersulfone resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd., and the like. Specific examples of the polyphenylene ether resin include vinyl group-containing oligophenylene ether/styrene resin "OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Company, Inc.

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

Among them, phenoxy resin and polyvinyl acetal resin are preferable as the thermoplastic resin. Accordingly, in one preferred embodiment, the thermoplastic resin comprises one or more selected from the group consisting of phenoxy resins and polyvinyl acetal resins. Among them, a phenoxy resin is preferable as the thermoplastic resin, and a phenoxy resin having a weight average molecular weight of 40,000 or more is particularly preferable. The use of a phenoxy resin having a weight average molecular weight of 40,000 or more enables miniaturization of wiring circuits.

When the resin composition contains a thermoplastic resin, the content of the thermoplastic resin is preferably 1 to 10% by mass, and 1.5 to 5% by mass, when the nonvolatile component in the resin composition is 100% by mass. is more preferable, and 2% by mass to 5% by mass is even more preferable.

<(H) flame retardant>
In one embodiment, the resin composition may contain (H) a flame retardant. Examples of flame retardants include organic phosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicone flame retardants, and metal hydroxides. A flame retardant may be used individually by 1 type, or may use 2 or more types together.

As the flame retardant, a commercially available product may be used, and examples thereof include “HCA-HQ” manufactured by Sanko Co., Ltd., and “PX-200” manufactured by Daihachi Chemical Industry Co., Ltd. As the flame retardant, one that is difficult to hydrolyze is preferable, and for example, 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide is preferable.

When the resin composition contains a flame retardant, the content of the flame retardant is preferably 0.5 to 20% by mass, and 0.5 to 15% by mass, when the nonvolatile component in the resin composition is 100% by mass. is more preferred, and 0.5 to 10% by mass is even more preferred.

<(I) Organic filler>
In one embodiment, the resin composition may contain (I) an organic filler. By containing the component (I), the tensile breaking strength of the cured product of the resin composition layer of the adhesive film can be improved. Any organic filler that can be used in forming the insulating layer of a printed wiring board may be used as the organic filler, and examples thereof include rubber particles, polyamide fine particles, silicone particles, and the like.

Commercially available rubber particles may be used, and examples thereof include "EXL2655" manufactured by Dow Chemical Japan, "AC3401N" and "AC3816N" manufactured by Aica Kogyo Co., Ltd., and the like.

When the resin composition contains an organic filler, the content of the organic filler is preferably 0.1 to 20% by mass, and 0.2 to 10% by mass when the non-volatile component in the resin composition is 100% by mass. % by mass is more preferred, and 0.3 to 5% by mass, or even more preferably 0.5 to 3% by mass.

<(J) Optional Additives>
In one embodiment, the resin composition may further contain other additives as necessary, and examples of such other additives include organic copper compounds, organic zinc compounds, and organic cobalt compounds. and resin additives such as thickeners, antifoaming agents, leveling agents, adhesion imparting agents, and coloring agents.

<Physical properties and applications of the resin composition>
INDUSTRIAL APPLICABILITY The resin composition of the present invention has a low dielectric loss tangent, good adhesion to plating and adhesion to a substrate, can provide an insulating layer excellent in smear removal properties, and has good compatibility. Therefore, the resin composition of the present invention can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (a resin composition for an insulating layer of a printed wiring board), and can be used for interlayer insulation of a printed wiring board. It can be used more preferably as a resin composition for forming a layer (a resin composition for an interlayer insulation layer of a printed wiring board). Moreover, since the resin composition of the present invention provides an insulating layer having good component embedding properties, it can be suitably used when the printed wiring board is a component built-in circuit board.

A cured product obtained by thermally curing the resin composition at 190° C. for 90 minutes exhibits a characteristic of low dielectric loss tangent. That is, it results in an insulating layer with a low dielectric loss tangent. The dielectric loss tangent is preferably 0.005 or less, more preferably 0.0045 or less, still more preferably 0.004 or less. Although the lower limit is not particularly limited, it may be 0.0001 or more. The dielectric loss tangent can be measured according to the method described in <Measurement of dielectric loss tangent> below.

A cured product obtained by thermally curing the resin composition at 190° C. for 90 minutes exhibits excellent adhesion (plating adhesion) to a conductor layer made of plating or the like. That is, it provides an insulating layer that exhibits good plating adhesion. The plating adhesion is preferably over 0.3 kgf/cm, more preferably 0.31 kgf/cm or more, and still more preferably 0.32 kgf/cm or more. Although the upper limit is not particularly limited, it may be 10 kgf/cm or less, or 1 kgf/cm or less. The plating adhesion can be measured according to the method described in <Measurement of plating adhesion> described later.

A cured product obtained by thermally curing the resin composition at 190° C. for 90 minutes exhibits excellent adhesion to a copper foil or the like (adhesion to a substrate). That is, it provides an insulating layer exhibiting good adhesion to the substrate. The substrate adhesion is preferably over 0.3 kgf/cm, more preferably 0.31 kgf/cm or more, and still more preferably 0.32 kgf/cm or more. Although the upper limit is not particularly limited, it may be 10 kgf/cm or less, or 1 kgf/cm or less. The adhesion to the substrate can be measured according to the method described in <Measurement of adhesion to the substrate> described below.

A cured product obtained by thermally curing the resin composition at 190° C. for 90 minutes exhibits the characteristic that smear generated during via hole formation can be easily removed (excellent smear removability). That is, it provides an insulating layer that exhibits good smear removal properties. The maximum smear length measured from the wall surface side of the bottom of the via hole is preferably less than 3 μm, more preferably 2.5 μm or less, and even more preferably 2 μm or less, because of its excellent smear removability. Although the lower limit is not particularly limited, it may be 0.01 μm or more. The smear removal property can be measured according to the method described in <Evaluation of smear removal property at the bottom of a via hole> described later.

Since the resin composition contains a predetermined amount of component (C), it exhibits excellent compatibility. Since the compatibility is excellent, precipitation of coarse particles of preferably 30 μm or more (more preferably 40 μm or more, still more preferably 50 μm or more) and oil droplets are not observed in the resin composition.

[Sheet-like base material]
Although the resin composition of the present invention can be applied in the form of a varnish, it is industrially preferably used in the form of a sheet-like substrate containing the resin composition. As the sheet-like base material, the following adhesive films and prepregs are preferable.

<Adhesive film>
In one embodiment, the adhesive film includes a support and a resin composition layer provided on the support, and the resin composition layer is formed from the resin composition of the present invention.

The thickness of the resin composition layer is preferably 100 μm or less, more preferably 80 μm or less, still more preferably 60 μm or less, and still more preferably 50 μm or less or 40 μm or less, from the viewpoint of thinning the printed wiring board. Although the lower limit of the thickness of the resin composition layer is not particularly limited, it can be usually 1 μm or more, 5 μm or more, or 10 μm or more.

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 polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"). ), polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketones, polyimides, 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, with copper foil being preferred. As the copper foil, a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. may be used.

The support may be subjected to matte treatment, corona treatment, or antistatic treatment on the surface to be bonded to the resin composition layer.

Further, as the support, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer may be used. The release agent used in the release layer of the release layer-attached support includes, for example, one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. . As the support with a release layer, a commercially available product may be used, for example, "SK-1", " AL-5", "AL-7", Toray's "Lumirror T60", Teijin's "Purex", and Unitika's "Unipeel".

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. When a release layer-attached support is used, the thickness of the release layer-attached support as a whole is preferably within the above range.

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

Organic solvents include, for example, ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone, acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, cellosolve and butyl carbitol. carbitols, aromatic hydrocarbons such as toluene and xylene, amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

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

In the adhesive film, a protective film conforming to the support can be further laminated on the surface of the resin composition layer that is not bonded to the support (that is, the surface opposite to the support). Although the thickness of the protective film is not particularly limited, it is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to prevent dust from adhering to the surface of the resin composition layer and scratches on the surface of the resin composition layer. The adhesive film can be wound into a roll and stored. When the adhesive film has a protective film, it can be used by peeling off the protective film.

<Prepreg>
In one embodiment, the prepreg is formed by impregnating a sheet-like fiber base material with the resin composition of the present invention.

The sheet-like fiber base material used for the prepreg is not particularly limited, and those commonly used as base materials for prepreg, such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric, can be used. From the viewpoint of thinning the printed wiring board, the thickness of the sheet-like fiber base material is preferably 50 μm or less, more preferably 40 μm or less, still more preferably 30 μm or less, and even more preferably 20 μm or less. Although the lower limit of the thickness of the sheet-like fiber base material is not particularly limited, it is usually 10 μm or more.

A prepreg can be manufactured by a known method such as a hot melt method or a solvent method.

The thickness of the prepreg can be in the same range as the resin composition layer in the adhesive film described above.

[Printed wiring board, method for manufacturing printed wiring board]
The printed wiring board of the present invention includes an insulating layer, a first conductor layer, and a second conductor layer formed from the cured resin composition of the present invention. The insulating layer is provided between the first conductor layer and the second conductor layer, and insulates the first conductor layer from the second conductor layer (the conductor layer is sometimes called a wiring layer). be).

The thickness of the insulating layer between the first and second conductor layers is preferably 6 μm or less, more preferably 5.5 μm or less, still more preferably 5 μm or less. Although the lower limit is not particularly limited, it can be 0.1 μm or more. The distance between the first conductor layer and the second conductor layer (the thickness of the insulating layer between the first and second conductor layers) is, as shown in FIG. 11 and the thickness t1 of the insulating layer 3 between the main surface 21 of the second conductor layer 2 . The first and second conductor layers are conductor layers adjacent to each other with an insulating layer interposed therebetween, and the main surfaces 11 and 21 face each other. The thickness of the insulating layer between the first and second conductor layers can be measured according to the method described later in <Measurement of Distance Between Conductor Layers (Thickness of Insulating Layer Between Conductor Layers)>.

The thickness t2 of the entire insulating layer is preferably 30 μm or less, more preferably 20 μm or less, and even more preferably 15 μm or less, or 10 μm or less. Although the lower limit is not particularly limited, it can be usually 1 μm or more, 1.5 μm or more, 2 μm or more, or the like.

A printed wiring board can be manufactured by a method including the following steps (I) and (II) using the adhesive film described above.
(I) Step of laminating the resin composition layer of the adhesive film on the inner layer substrate so as to be bonded to the inner layer substrate (II) Step of thermally curing the resin composition layer to form an insulating layer

The "inner layer substrate" used in step (I) mainly means a substrate such as a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, or a substrate having A circuit board on which a patterned conductor layer (circuit) is formed. The term "inner layer substrate" as used in the present invention also includes an inner layer circuit board that is an intermediate product on which an insulating layer and/or a conductor layer are to be further formed when manufacturing a printed wiring board. When the printed wiring board is a circuit board with built-in components, an inner layer board with built-in components can be used.

The lamination of the inner layer substrate and the adhesive film can be performed, for example, by thermocompression bonding the adhesive film to the inner layer substrate from the support side. Examples of the member for thermocompression bonding the adhesive film to the inner layer substrate (hereinafter also referred to as “thermocompression member”) include heated metal plates (such as SUS end plates) and metal rolls (SUS rolls). Instead of directly pressing the thermocompression member onto the adhesive film, it is preferable to press the adhesive film through an elastic material such as heat-resistant rubber so that the adhesive film can sufficiently follow the unevenness of the surface of the inner layer substrate.

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

Lamination can be done with a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum pressurized laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nikko Materials, a batch-type vacuum pressurized laminator, and the like.

After lamination, the laminated adhesive film may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression member from the support side. Pressing conditions for the smoothing treatment may be the same as the thermocompression bonding conditions for the lamination described above. Smoothing treatment can be performed with a commercially available laminator. Lamination and smoothing may be performed continuously using the above-mentioned commercially available vacuum laminator.

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

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

The thermosetting conditions for the resin composition layer are not particularly limited, and conditions that are commonly used for forming insulating layers of printed wiring boards may be used.

For example, the thermosetting conditions for the resin composition layer vary depending on the type of resin composition, etc., but the curing temperature is in the range of 120° C. to 240° C. (preferably in the range of 150° C. to 220° C., more preferably in the range of 170° C. to 200° C. range) and the curing time can be in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 minutes).

Before thermosetting the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermosetting the resin composition layer, the resin composition layer is cured at a temperature of 50° C. or more and less than 120° C. (preferably 60° C. or more and 110° C. or less, more preferably 70° C. or more and 100° C. or less). Preheating may be performed for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

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

Step (III) is a step of making holes in the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. Step (III) may be performed using, for example, a drill, laser, plasma, or the like, depending on the composition of the resin composition used to form the insulating layer. The dimensions and shape of the holes may be appropriately determined according to the design of the printed wiring board.

Step (IV) is a step of roughening the insulating layer. The procedure and conditions of the roughening treatment are not particularly limited, and known procedures and conditions that are commonly used in forming insulating layers of printed wiring boards can be employed. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralizing treatment with a neutralizing liquid in this order. The swelling liquid used for the roughening treatment is not particularly limited, but examples thereof include alkaline solutions, surfactant solutions, etc., preferably alkaline solutions, more preferably sodium hydroxide solutions and potassium hydroxide solutions. preferable. Examples of commercially available swelling liquids include "Swelling Dip Securigans P" and "Swelling Dip Securigans SBU" manufactured by Atotech Japan. The swelling treatment with the swelling liquid is not particularly limited, but can be performed, for example, by immersing the insulating layer in the swelling liquid at 30.degree. C. to 90.degree. C. for 1 to 20 minutes. From the viewpoint of suppressing swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40° C. to 80° C. for 5 minutes to 15 minutes. The oxidizing agent used in the roughening treatment is not particularly limited, but examples thereof include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated to 60° C. to 80° C. for 10 to 30 minutes. Further, the permanganate concentration in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Security P" manufactured by Atotech Japan. Moreover, as a neutralization liquid used for the roughening treatment, an acidic aqueous solution is preferable, and as a commercial product, for example, "Reduction Solution Securigant P" manufactured by Atotech Japan Co., Ltd. can be mentioned. The treatment with the neutralizing solution can be carried out by immersing the treated surface roughened with the oxidizing agent in the neutralizing solution at 30° C. to 80° C. for 5 to 30 minutes. From the viewpoint of workability, etc., a method of immersing an object roughened with an oxidizing agent in a neutralizing solution at 40° C. to 70° C. for 5 to 20 minutes is preferable.

In one embodiment, the arithmetic mean roughness Ra of the insulating layer surface after the roughening treatment is preferably 400 nm or less, more preferably 350 nm or less, and even more preferably 300 nm or less. Although the lower limit is not particularly limited, it is preferably 0.5 nm or more, more preferably 1 nm or more. The root-mean-square roughness Rq of the insulating layer surface after the roughening treatment is preferably 400 nm or less, more preferably 350 nm or less, and even more preferably 300 nm or less. Although the lower limit is not particularly limited, it is preferably 0.5 nm or more, more preferably 1 nm or more. The arithmetic mean roughness (Ra) and root mean square roughness (Rq) of the insulating layer surface can be measured using a non-contact surface roughness meter.

Step (V) is a step of forming a conductor layer. When no conductor layer is formed on the inner layer substrate, the step (V) is a step of forming a first conductor layer, and when a conductor layer is formed on the inner layer substrate, the conductor layer becomes the first conductor layer. and step (V) is a step of forming a second conductor layer.

The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer contains one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Contains metal. The conductor layer may be a single metal layer or an alloy layer, and the alloy layer may be, for example, an alloy of two or more metals selected from the above group (for example, a nickel-chromium alloy, a copper- nickel alloys and copper-titanium alloys). Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, etc., single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, nickel-chromium alloys, copper- Nickel alloys and copper/titanium alloy alloy layers are preferred, and single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel/chromium alloy alloy layers are more preferred, and copper single metal layers are preferred. A metal layer is more preferred.

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

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

In one embodiment, the conductor layer may be formed by plating. For example, a conductive layer having a desired wiring pattern can be formed by plating the surface of the insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method. An example of forming a conductor layer by a semi-additive method is shown below.

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer to expose a portion of the plating seed layer corresponding to a desired wiring pattern. After forming a metal layer on the exposed plating seed layer by electroplating, the mask pattern is removed. After that, the unnecessary plating seed layer is removed by etching or the like, and a conductor layer having a desired wiring pattern can be formed.

Since the adhesive film of the present invention provides an insulating layer with good component embedding properties, it can be suitably used even when the printed wiring board is a circuit board with built-in components. A circuit board with a built-in component can be manufactured by a known manufacturing method.

A printed wiring board manufactured using the adhesive film of the present invention is provided with an insulating layer that is a cured product of the resin composition layer of the adhesive film, and an embedded wiring layer embedded in the insulating layer. good too.

In other embodiments, printed wiring boards can be manufactured using the prepregs described above. The manufacturing method is basically the same as in the case of using an adhesive film.

[Semiconductor device]
A semiconductor device of the present invention includes the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.

Examples of semiconductor devices include various semiconductor devices used in electrical appliances (eg, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (eg, motorcycles, automobiles, trains, ships, aircraft, etc.).

The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. A "conducting part" is a "part where an electric signal is transmitted on a printed wiring board", and the place may be a surface or an embedded part. Also, the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

The method of mounting a semiconductor chip when manufacturing a semiconductor device is not particularly limited as long as the semiconductor chip functions effectively. (BBUL) mounting method, anisotropic conductive film (ACF) mounting method, non-conductive film (NCF) mounting method, and the like. Here, "a mounting method using a build-up layer without bumps (BBUL)" refers to a "mounting method in which a semiconductor chip is directly embedded in a concave portion of a printed wiring board and the semiconductor chip and wiring on the printed wiring board are connected." is.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to Examples. The invention is not limited to these examples. In the following, "parts" and "%" mean "mass parts" and "mass%", respectively, unless otherwise specified.

<Example 1>
40 parts of bixylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185) was heated and dissolved in 30 parts of solvent naphtha with stirring, and then cooled to room temperature. 330 parts of an inorganic filler (“SO-C2” manufactured by Admatechs, average particle diameter 0.5 μm, carbon amount per unit surface area 0.38 mg/m ² ) was mixed and kneaded and dispersed by a triple roll. Thereto, 92.3 parts of an active ester curing agent ("HPC-8000-65T" manufactured by DIC, a toluene solution with an active group equivalent weight of about 223 and a non-volatile content of 65%), a compound having a 5-membered or higher cyclic ether structure ("A-DOG" manufactured by Shin-Nakamura Chemical Co., Ltd.) 15 parts, indene cumarone resin ("H-100" manufactured by Nikko Chemical Co., Ltd.) 5 parts, 4-dimethylaminopyridine (DMAP) as a curing accelerator 5% 2 parts of MEK solution and 0.13 parts of dicumyl peroxide (“Percumyl D” manufactured by NOF Corporation) were mixed and uniformly dispersed in a rotating mixer to prepare resin varnish 1.

Resin varnish 1 is applied on the release surface of a polyethylene terephthalate film with alkyd release treatment (PET film, “AL-5” manufactured by Lintec Corporation, thickness 38 μm), and the thickness of the resin composition layer after drying is 40 μm. The adhesive film 1 was prepared by uniformly coating the adhesive with a die coater and drying at 80 to 110° C. (average 95° C.) for 5 minutes.

<Example 2>
In Example 1, the bixylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185) was changed from 40 parts to 25 parts, and the inorganic filler ("SO-C2" manufactured by Admatechs, average particle size diameter 0.5 μm, amount of carbon per unit surface area 0.38 mg/m ² ) was changed from 330 parts to 320 parts, and an active ester curing agent ("HPC-8000-65T" manufactured by DIC, active group equivalent of about 223 A toluene solution with a non-volatile content of 65%) was changed from 92.3 parts to 61.5 parts, and a compound having a 5-membered or higher cyclic ether structure (Shin-Nakamura Chemical Co., Ltd. "A-DOG") was added to 15 parts. changed to 40 copies. A resin varnish 2 and an adhesive film 2 were produced in the same manner as in Example 1 except for the above matters.

<Example 3>
In Example 1, the compound having a 5-membered or more cyclic ether structure (“A-DOG” manufactured by Shin-Nakamura Chemical Co., Ltd.) was changed from 15 parts to 1.5 parts, and bixylenol-type epoxy resin (Mitsubishi Chemical Co., Ltd. "YX4000HK", epoxy equivalent of about 185) was changed from 40 parts to 45 parts, and an active ester curing agent ("HPC-8000-65T" manufactured by DIC Corporation, a toluene solution with a nonvolatile content of 65% with an active group equivalent of about 223 ) was changed from 92.3 parts to 84.6 parts, and 22.5 parts of a thermoplastic resin ("OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Co., Ltd., a toluene solution with a non-volatile content of 60%) was mixed. A resin varnish 3 and an adhesive film 3 were produced in the same manner as in Example 1 except for the above matters.

<Example 4>
In Example 1, the bixylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185) was changed from 40 parts to 20 parts, and the inorganic filler ("SO-C2" manufactured by Admatechs, average particle size diameter 0.5 μm, amount of carbon per unit surface area 0.38 mg/m ² ) was changed from 330 parts to 310 parts, and an active ester curing agent ("HPC-8000-65T" manufactured by DIC, active group equivalent of about 223 Toluene solution with a non-volatile content of 65%) was changed from 92.3 parts to 46.2 parts, and a compound having a 5-membered or higher cyclic ether structure (Shin-Nakamura Chemical Co., Ltd. "A-DOG") was added to 15 parts. to 50 copies. A resin varnish 4 and an adhesive film 4 were produced in the same manner as in Example 1 except for the above matters.

<Comparative Example 1>
In Example 1, the bixylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185) was changed from 40 parts to 20 parts, and the inorganic filler ("SO-C2" manufactured by Admatechs, average particle size diameter 0.5 μm, amount of carbon per unit surface area 0.38 mg/m ² ) was changed from 330 parts to 310 parts, and an active ester curing agent ("HPC-8000-65T" manufactured by DIC, active group equivalent of about 223 Toluene solution with a non-volatile content of 65%) was changed from 92.3 parts to 46.2 parts, and a compound having a 5-membered or higher cyclic ether structure (Shin-Nakamura Chemical Co., Ltd. "A-DOG") was added to 15 parts. to 60 copies. A resin varnish 5 and an adhesive film 5 were produced in the same manner as in Example 1 except for the above matters.

<Comparative Example 2>
In Example 3, the compound having a 5-membered or more cyclic ether structure (“A-DOG” manufactured by Shin-Nakamura Chemical Co., Ltd.) was changed from 1.5 parts to 0.5 parts, and the thermoplastic resin (Mitsubishi Gas Chemical "OPE-2St 1200" manufactured by Co., Ltd., a toluene solution with a non-volatile content of 60%) was changed from 22.5 parts to 24.2 parts. A resin varnish 6 and an adhesive film 6 were produced in the same manner as in Example 3 except for the above matters.

<Comparative Example 3>
In Example 1, 15 parts of a compound having a 5-membered or more cyclic ether structure (manufactured by Shin-Nakamura Chemical Co., Ltd. "A-DOG") was added to 15 parts of a resin having a vinyl group (manufactured by Shin-Nakamura Chemical Co., Ltd. "23G"). changed to department. A resin varnish 7 and an adhesive film 7 were produced in the same manner as in Example 1 except for the above matters.

<Comparative Example 4>
In Example 1, 15 parts of a compound having a 5-membered or more cyclic ether structure (“A-DOG” manufactured by Shin-Nakamura Chemical Co., Ltd.) was added to a resin having a vinyl group (“A-DCP” manufactured by Shin-Nakamura Chemical Co., Ltd. ) changed to 15 copies. A resin varnish 8 and an adhesive film 8 were produced in the same manner as in Example 1 except for the above matters.

<Comparative Example 5>
In Example 1, 15 parts of a compound having a 5-membered or more cyclic ether structure (“A-DOG” manufactured by Shin-Nakamura Chemical Co., Ltd.) was added to a thermoplastic resin (“OPE-2St 1200” manufactured by Mitsubishi Gas Chemical Co., Ltd., non-volatile 60% toluene solution) to 25 parts. A resin varnish 9 and an adhesive film 9 were produced in the same manner as in Example 1 except for the above matters.

[Evaluation method]
<Preparation of sample for evaluation of cured physical properties>
The adhesive films obtained in Examples and Comparative Examples were thermally cured at 190° C. for 90 minutes, and the PET film of the support was peeled off to prepare a sheet-like cured product evaluation sample.

<Measurement of dielectric loss tangent>
A test piece having a width of 2 mm and a length of 80 mm was cut out from the cured product evaluation sample. The dielectric loss tangent of the cut test piece was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23 ° C. by a cavity resonance perturbation method using a measurement device "HP8362B" manufactured by Agilent Technologies. evaluated according to the standard.

<Evaluation of compatibility>
The resin composition layer side of the adhesive films prepared in Examples and Comparative Examples was observed with a microscope (“DIGITAL MICROSCOPE KH-8700” manufactured by Hylox Co., Ltd.) in an area of 1 cm ² to confirm the presence or absence of coarse particles. and evaluated according to the following criteria.
Good: No deposition of coarse particles of 50 μm or more and no oil droplets observed in the resin composition layer.
Poor: Precipitation of coarse particles of 50 μm or more and oil droplets are observed in the resin composition layer.

<Preparation of evaluation substrate>
(1) Surface Treatment of Substrate A double-sided copper-clad laminate (copper foil thickness: 18 μm, substrate thickness: 0.4 mm, “R1515A” manufactured by Panasonic) with an inner layer circuit formed thereon was prepared. This laminate has a copper foil as a first conductor layer on its surface. Both surfaces of this laminate were immersed in "CZ8101" manufactured by MEC Co., Ltd. and etched by 1 μm to roughen the copper surface, thereby producing an inner layer circuit board.

(2) Lamination processing of adhesive film The adhesive films prepared in Examples and Comparative Examples are laminated using a batch-type vacuum pressure laminator (manufactured by Meiki Co., Ltd. “MVLP-500”) so that the resin composition layer is the inner layer circuit board. Both sides of the inner layer circuit board were laminated so as to be joined. The lamination process was carried out by pressure bonding for 30 seconds at 100° C. and pressure of 0.74 MPa after reducing the pressure to 13 hPa or less for 30 seconds. Thereafter, the resin composition layer was cured by heating in an oven at 190° C. for 90 minutes to obtain an insulating layer.

(3) Via hole formation Using a CO ₂ laser processing machine (LC-2E21B/1C) manufactured by Hitachi Via Mechanics Co., Ltd., mask diameter 1.60 mm, focus offset value 0.050, pulse width 25 μs, power 0.66 W, aperture 13 , the number of shots was 2, and a part of the insulating layer was irradiated with a laser beam under the conditions of burst mode, and a hole was formed in the part of the insulating layer. The top diameter (diameter) of the hole (via hole) formed by drilling was 50 μm. After that, the PET film as the support was peeled off.

(4) Roughening Treatment The internal circuit board on which the insulating layer was formed was subjected to wet roughening treatment using a surface treatment agent kit including a swelling liquid, an oxidizing agent, and a neutralizing liquid. Specifically, the internal circuit board on which the insulating layer is formed is placed in a swelling liquid, Swelling Dip Securigant P (an aqueous solution of glycol ethers and sodium hydroxide) containing diethylene glycol monobutyl ether manufactured by Atotech Japan Co., Ltd. at 60°C. for 10 minutes, then immersed in Concentrate Compact P (KMnO ₄ : 60 g / L, NaOH: 40 g / L aqueous solution) manufactured by Atotech Japan as an oxidizing agent at 80 ° C. for 20 minutes, and finally neutralized As a liquid, it was immersed in Reduction Shoryusin Securigant P (an aqueous solution of sulfuric acid) manufactured by Atotech Japan Co., Ltd. at 40° C. for 5 minutes, and then dried at 80° C. for 30 minutes. The obtained substrate was designated as an evaluation substrate A.

(5) Plating by Semi-Additive Method Evaluation board A was immersed in an electroless plating solution containing PdCl ₂ at 40° C. for 5 minutes, and then immersed in an electroless copper plating solution at 25° C. for 20 minutes. The immersed evaluation substrate A was heated at 150° C. for 30 minutes for annealing treatment, and then subjected to copper sulfate electroplating to form a second conductor layer with a thickness of 30 μm. The obtained evaluation substrate A having the second conductor layer was annealed at 190° C. for 60 minutes, and the resulting substrate was used as an evaluation substrate B.

<Measurement of plating adhesion>
In the second conductor layer of the evaluation board B, a cut of 10 mm in width and 100 mm in length is made, and one end is peeled off and a gripping tool (manufactured by TSE Co., Autocom type testing machine AC-50C-SL ), and the load (kgf/cm) when peeling off 35 mm in the vertical direction at a rate of 50 mm/min at room temperature (25° C.) was measured and evaluated according to the following criteria.

<Evaluation of Smear Removability at Bottom of Via Hole>
The periphery of the via hole bottom of the evaluation substrate A was observed with a scanning electron microscope (SEM), and the maximum smear length from the wall surface side of the via hole bottom was measured from the obtained image. Here, the "maximum smear length" means the maximum length of smear from the circumference of the bottom surface of the via to the center of the circle. Evaluation is as follows.
Good: Maximum smear length is less than 3 μm Bad: Maximum smear length is 3 μm or more

<Measurement of substrate adhesion>
(1) Surface treatment of copper foil The glossy surface of “3EC-III” (electrolytic copper foil, 35 μm) manufactured by Mitsui Kinzoku Mining Co., Ltd. is immersed in MEC Etch Bond “CZ-8101” manufactured by MEC Co., Ltd. to roughen the copper surface. (Ra value = 1 µm), and an antirust treatment (CL8300) was applied. This copper foil is called CZ copper foil. Further, heat treatment was performed in an oven at 130° C. for 30 minutes.

(2) Lamination of copper foil and formation of insulating layer The adhesive films prepared in Examples and Comparative Examples are batch-type vacuum pressure laminator (“MVLP-500” manufactured by Meiki Co., Ltd.), and the resin composition layer is the inner layer. Both sides of the inner layer circuit board were laminated so as to be bonded to the circuit board. The lamination process was carried out by pressure bonding for 30 seconds at 100° C. and pressure of 0.74 MPa after reducing the pressure to 13 hPa or less for 30 seconds. The PET film as the support was peeled off from the laminated adhesive film. The treated surface of the "3EC-III" CZ copper foil was laminated under the same conditions as above on the resin composition layer from which the support had been peeled off. Then, a sample was produced by curing the resin composition layer under curing conditions of 190° C. for 90 minutes to form an insulating layer.

(3) Measurement of Copper Foil Peeling Strength (Adhesion) The prepared sample was cut into small pieces of 150×30 mm. Using a cutter, cut the copper foil portion of the small piece with a width of 10 mm and a length of 100 mm. AC-50C-SL"), and using an Instron universal testing machine, at room temperature, measure the load when peeling off 35 mm in the vertical direction at a speed of 50 mm / min in accordance with JIS C6481. , was evaluated according to the following criteria.

The results of the examples and comparative examples described above are shown in the table below. In the table below, the abbreviations have the following meanings.
YX4000HK: bixylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation)
HPC-8000-65T: Active ester curing agent ("HPC-8000-65T" manufactured by DIC)
A-DOG: dioxane acrylic monomer (“A-DOG” manufactured by Shin-Nakamura Chemical Co., Ltd.)
A-DCP: dicyclopentane acrylic monomer ("A-DCP" manufactured by Shin-Nakamura Chemical Co., Ltd.)
23G: Ethylene oxide acrylic monomer (“23G” manufactured by Shin-Nakamura Chemical Co., Ltd.)
OPE-2St 1200: Thermoplastic resin ("OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Co., Ltd.)
H-100: Indene cumarone resin ("H-100" manufactured by Nikko Chemical Co., Ltd.)
SO-C2: Spherical silica ("SO-C2" manufactured by Admatechs)
Parkmil D: dicumyl peroxide (manufactured by NOF Corporation)
DMAP: 4-dimethylaminopyridine In the table, the blending amount is a solid content conversion value, "content of component (A) (% by mass)", "content of component (B) (% by mass)", and "(C) component content (% by mass)" represents the content when the resin component is 100% by mass.

From the results of Table 1, Examples 1 to 4 containing components (A) to (C) and containing a predetermined amount of component (C) have dielectric loss tangent, compatibility, plating adhesion, substrate adhesion, and smear It can be seen that all of the removability is excellent.

On the other hand, in Comparative Example 1, which contains components (A) to (C) but the content of component (C) exceeds 50% by mass when the resin component is 100% by mass, plating adhesion and substrate adhesion are performed. It can be seen that it is inferior to Examples 1-4.
Comparative Example 2, which contains components (A) to (C), but the content of component (C) is less than 1% by mass when the resin component is 100% by mass, has smear removal properties comparable to those of Examples 1 to 4. I know it's inferior.
It can be seen that Comparative Example 3, which does not contain component (C), is inferior to Examples 1 to 4 in dielectric loss tangent.
Also, in Comparative Examples 4 and 5, which did not contain component (C), the dielectric loss tangent, plating adhesion, base adhesion, and smear removal properties could not be measured due to poor compatibility.

In Examples 1 to 4, even if the components (D) to (G) are not contained, it has been confirmed that the same results as in the above examples are obtained although there is a difference in degree.

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

Claims (11)

A resin composition comprising (A) an epoxy resin, (B) an epoxy resin curing agent, (C) a compound having a 5-membered or more cyclic ether structure , ( D) an inorganic filler , and (E) a curing accelerator. hand,
(B) component is an active ester curing agent,
Component (C) has one or more functional groups selected from the group consisting of vinyl groups and methacrylic groups, and the vinyl groups are selected from the group consisting of acrylic groups, allyl groups, and styryl groups 1 A group contained in at least one functional group,
(D) component is silica,
The content of the component (A) is 5% by mass to 50% by mass when the resin component is 100% by mass,
The content of the component (B) is 5% by mass or more and 60% by mass or less when the non-volatile components constituting the resin composition excluding the component (D) is taken as 100% by mass,
The content of the component (C) is 1% by mass to 50% by mass when the component excluding the component (D) among the non-volatile components constituting the resin composition is 100% by mass,
(D) The content of the component is 50% by mass or more when the non-volatile component of the resin composition is 100% by mass,
A resin composition for forming an insulating layer that is used in a step of boring a hardened insulating layer and a step of roughening the insulating layer. 2. The resin composition according to claim 1 , wherein component (C) contains a dioxane structure. 3. The resin composition according to claim 1 , wherein the component (C) has a vinyl group. The resin composition according to any one of claims 1 to 3 , wherein component (C) is the following compound.

The resin composition according to any one of claims 1 to 4 , wherein the step of roughening the insulating layer is a step of swelling the insulating layer with a swelling liquid and then roughening the insulating layer. The resin composition according to any one of claims 1 to 5 , wherein the insulating layer is an insulating layer of a printed wiring board. The resin composition according to any one of claims 1 to 5 , wherein the insulating layer is an interlayer insulating layer of a printed wiring board. A sheet-like substrate comprising the resin composition according to any one of claims 1 to 5 . An adhesive film comprising a support and a resin composition layer formed of the resin composition according to any one of claims 1 to 7 provided on the support. 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,
A printed wiring board, wherein the insulating layer is a cured product of the resin composition according to any one of claims 1 to 7 . A semiconductor device comprising the printed wiring board according to claim 10 .

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