KR20190084890A - Resin composition - Google Patents

Abstract

The present invention relates to a resin composition which is capable of obtaining a cured product having low dielectric loss and having excellent smear removal properties, to a resin sheet having a resin composition layer including the resin composition, to a printed wiring board including an insulation layer formed by the cured product of the resin composition and to a semiconductor device including the cured product of the resin composition. The resin composition comprises: (A) an aromatic hydrocarbon resin containing an aromatic ring as a single ring or a condensed ring and having two or more groups containing an oxygen atom coupled with the aromatic ring per unit; and (B) an active ester-based curing agent.

Description

Resin composition {RESIN COMPOSITION}

The present invention relates to a resin composition. The present invention also relates to a resin sheet, a printed wiring board and a semiconductor device using the resin composition.

In recent years, miniaturization and high performance of electronic devices have progressed. In a multilayer printed wiring board, the buildup layer has been layered, requiring miniaturization and high density wiring, and insulating materials with low dielectric tangent are required for reduction of transmission loss.

For example, Patent Document 1 discloses a resin composition containing (A) an epoxy resin, (B) an active ester compound, and (C) a smear suppressing component, and when the nonvolatile component of the resin composition is 100 mass% , And (C) 0.001 to 10% by mass of a smear inhibiting component.

Japanese Patent Application Laid-Open No. 2014-5464

When the insulating layer of the multilayered printed circuit board is perforated, smear (resin residue) is generated in the via hole, and smear is required to be removed in the roughening process. However, the inventors of the present invention have found that the multilayer printed circuit board using the low dielectric loss tangent resin composition containing the active ester compound is used to produce smear in the via hole Resin residue) is sometimes insufficient, and it is found that the smaller the diameter of the via-hole becomes, the more difficult it becomes.

Accordingly, a problem to be solved by the present invention is to provide a resin composition capable of obtaining a cured product having a low dielectric tangent and an excellent smear removal property; A resin sheet having a resin composition layer containing the resin composition; A printed wiring board including an insulating layer formed of a cured product of the resin composition; And a semiconductor device including the cured product of the resin composition.

As a result of intensive studies to solve the above problems, the present inventors have found that (A) an aromatic ring containing an aromatic ring as a single ring or condensed ring, and a group containing an oxygen atom bonded to the aromatic ring per one (C) an active ester-based curing agent, the present inventors have accomplished the present invention by finding out that the above problems can be solved by a resin composition comprising a combination of two or more aromatic hydrocarbon resins and (C) an active ester-based curing agent.

That is, the present invention includes the following contents.

(1) An aromatic ring hydrocarbon resin composition comprising (A) an aromatic ring hydrocarbon resin containing an aromatic ring as a monocyclic or condensed ring and having two or more groups containing oxygen atoms bonded to the aromatic ring per one aromatic ring, and

(B) an active ester-based curing agent.

[2] The resin composition according to [1], wherein the component (A) has a structure represented by the following formula (1).

In Formula 1,

R ¹¹ each independently represents a monovalent group.

[3] The resin composition according to [1] or [2], wherein the component (A) has a structure represented by the following formula (2).

In Formula 2,

R ²¹ each independently represents a monovalent group.

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

In Formula 3,

R ³¹ each independently represents a monovalent group,

R ³² each independently represents a divalent hydrocarbon group,

n3 is an integer of 0 to 10;

[5] The resin composition according to any one of [1] to [4], wherein the component (A) is represented by the following formula (6).

In Formula 6,

R ⁶¹ each independently represents a monovalent group,

n6 is an integer of 0 to 10;

[6] The resin composition according to any one of [1] to [5], wherein the group containing an oxygen atom bonded to the aromatic ring is an epoxyalkyleneoxy group, an alkoxy group or a hydroxyl group.

[7] The resin composition according to any one of [1] to [6], further comprising (C) an epoxy resin.

[8] The resin composition according to [7], wherein the content of the component (A) is 5% by mass or more and 50% by mass or less when the total content of the component (A) and the component (C) is 100% by mass.

[9] The resin composition according to any one of [1] to [8], wherein the content of the component (B) is 1% by mass or more and 30% by mass or less when the nonvolatile component in the resin composition is 100% by mass.

[10] The resin composition according to any one of [1] to [9], further comprising (D) an inorganic filler.

[11] The resin composition according to [10], wherein the content of the component (D) is 50% by mass or more based on 100% by mass of the nonvolatile component in the resin composition.

[12] A resin composition according to any one of [1] to [11], which is a resin composition for forming an insulating layer of a multilayer printed wiring board.

[13] A resin composition according to any one of [1] to [12], which is a resin composition for forming an insulating layer having a via hole having a top diameter of 35 μm or less.

[14] A resin composition for forming an insulating layer having a via-hole having a thickness (탆) of an insulating layer and an aspect ratio (thickness of an insulating layer / top diameter) of a top diameter (탆) of 0.5 or more is selected from among [1] to [13] Lt; / RTI >

[15] A resin sheet comprising a support and a resin composition layer comprising the resin composition according to any one of [1] to [14] provided on the support.

[16] The resin sheet according to [15], wherein the resin composition layer has a thickness of 20 μm or less.

[17] A printed wiring board comprising an insulating layer formed by a cured product of the resin composition according to any one of [1] to [14].

[18] A semiconductor device comprising a printed wiring board according to [17].

According to the present invention, there can be provided a resin composition capable of obtaining a cured product having a low dielectric tangent and an excellent smear removal property; A resin sheet having a resin composition layer containing the resin composition; A printed wiring board including an insulating layer formed of a cured product of the resin composition; And a semiconductor device including the cured product of the resin composition.

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

[Resin composition]

The resin composition of the present invention comprises (A) an aromatic hydrocarbon resin containing an aromatic ring as a monocyclic or condensed ring and having two or more groups containing oxygen atoms bonded to the aromatic ring per one aromatic ring, and (B ) An active ester-based curing agent. By using such a resin composition layer, it is possible to obtain the desired effect of the present invention that a cured product having a low dielectric tangent and excellent smear removal property can be obtained. Therefore, the cured product of the resin composition can be preferably used as an insulating layer of a multilayer printed circuit board, taking advantage of its excellent properties.

The resin composition may further contain optional components in combination with the components (A) to (B). Examples of optional components include (C) an epoxy resin, (D) an inorganic filler, (F) a curing agent, (F) a thermoplastic resin, (G) a curing accelerator, and (H) other additives. Hereinafter, each component contained in the resin composition of the present invention will be described in detail.

<(A) An aromatic hydrocarbon resin containing an aromatic ring as a monocyclic or condensed ring, and having two or more groups containing an oxygen atom bonded to the aromatic ring per one aromatic ring>

The resin composition contains (A) an aromatic ring as a monocyclic or condensed ring, and contains, per one aromatic ring, an aromatic hydrocarbon resin having two or more groups containing an oxygen atom bonded to the aromatic ring. The aromatic ring is liable to be oxidized by electron donation of an oxygen atom in a group containing an oxygen atom bonded to the aromatic ring. Further, since two or more of these groups are contained per one aromatic ring, the aromatic rings are more likely to be oxidized. Therefore, since the component (A) is easily oxidized, the smear removal property of the cured product of the resin composition can be improved.

Here, the term &quot; aromatic ring &quot; includes any aromatic ring as a monocyclic ring such as a benzene ring and an aromatic ring as a condensed ring such as a naphthalene ring. The number of carbon atoms per one aromatic ring contained in the component (A) is preferably 6 or more, preferably 10 or more, and preferably 20 or less, more preferably 20 or more, from the viewpoint of obtaining a desired effect of the present invention More preferably 14 or less.

Examples of the aromatic ring include monocyclic rings such as a benzene ring and a biphenyl ring; Naphthalene ring and condensed ring such as anthracene ring, and condensed rings are preferable from the viewpoint of further improving the smear removal property. The type of the aromatic ring contained in one molecule of the aromatic hydrocarbon resin may be one kind or two or more types.

At least one of the aromatic rings contained in the aromatic hydrocarbon resin as the component (A) has two or more groups containing oxygen atoms bonded to the aromatic ring per one aromatic ring. The number of groups containing an oxygen atom bonded to an aromatic ring per aromatic ring is preferably 4 or less, more preferably 3 or less, particularly preferably 3 or less, particularly preferably 3 or less, from the viewpoint of obtaining a desired effect of the present invention. Two.

The number of aromatic rings having a group containing an oxygen atom bonded to two or more of these aromatic rings per one molecule of the component (A) is usually one or more, and from the viewpoint of obtaining a desired effect of the present invention remarkably, Two or more, and more preferably three or more. The upper limit is not particularly limited, but is preferably 6 or less, and more preferably 5 or less, from the viewpoint of suppressing steric hindrance and enhancing reactivity with the epoxy resin.

Examples of the group containing an oxygen atom bonded to the aromatic ring include an epoxyalkyleneoxy group, an alkoxy group, and a hydroxyl group. The alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 6 carbon atoms, and more preferably an alkoxy group having 1 to 3 carbon atoms, in view of obtaining the desired effect of the present invention remarkably And an alkoxy group (methoxy group) having 1 carbon atom is particularly preferable. The alkylene group in the epoxyalkyleneoxy group is preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms, from the viewpoint of obtaining the desired effect of the present invention remarkably. More preferably 1 (number of carbon atoms) (glycidyl ether group) is particularly preferable.

As the component (A), for example, an aromatic hydrocarbon resin having a structure represented by the following formula (1) is preferable.

[Chemical Formula 1]

In Formula 1,

R ¹¹ each independently represents a monovalent group.

In the general formula (1), each R ¹¹ independently represents a monovalent group. The group containing an oxygen atom bonded to the aromatic ring is "-OR ¹¹ " in the formula (1). Examples of the monovalent group include a hydrogen atom; A monovalent organic group such as an epoxy alkyl group and an optionally substituted alkyl group. The number of carbon atoms in the alkyl group and the alkyl group in the epoxy alkyl group is equal to the number of carbon atoms in the alkoxy group. Examples of the substituent of the alkyl group include a halogen atom, a hydroxyl group and an epoxy. Two or more substituents may be bonded to form a ring. Among them, R ¹¹ is preferably an epoxy alkyl group or a hydrogen atom, more preferably an epoxy alkyl group, and more preferably a glycidyl group, from the viewpoint of improving the smear removal property.

The structure represented by the formula (1) is preferably represented by the following formula (2).

(2)

In Formula 2,

R ²¹ each independently represents a monovalent group.

In the general formula (2), R ²¹ represents a monovalent group, and R ²¹ is the same as R ¹¹ in the general formula (1). A group containing an oxygen atom bonded to an aromatic ring at the 1-position and 6-position of the naphthalene ring is bonded to the aromatic ring as shown by the general formula (2), whereby smear removal can be further improved.

As the component (A), for example, an aromatic hydrocarbon resin represented by the following formula (3) is preferable.

(3)

In Formula 3,

R ³¹ each independently represents a monovalent group,

R ³² each independently represents a divalent hydrocarbon group,

n3 is an integer of 0 to 10;

In the formula (3), R ³¹ represents a monovalent group, and R ³¹ is the same as R ¹¹ in the formula (1).

In the general formula (3), R ³² represents a divalent hydrocarbon group. The divalent hydrocarbon group may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The number of carbon atoms of the divalent hydrocarbon group is usually 1 or more and is preferably 3 or more, more preferably 5 or more, further preferably 7 or more from the viewpoint of obtaining the desired effect of the present invention . The upper limit of the number of carbon atoms is preferably 20 or less, 15 or less, or 10 or less from the viewpoint of achieving the desired effect of the present invention.

Specific examples of R ³² include the following divalent hydrocarbon groups.

In the general formula (3), n3 represents an integer of 0 to 10. From the viewpoint of obtaining the desired effect of the present invention remarkably, n3 is preferably 0 or more, more preferably 2 or more, still more preferably 3 or more, preferably 10 or less, more preferably 5 or less .

The aromatic hydrocarbon resin represented by the general formula (3) is preferably an aromatic hydrocarbon resin represented by the following general formula (4).

In Formula 4,

R ⁴¹ each independently represents a monovalent group,

R &lt; ⁴² &gt; each independently represents an alkylene group,

n4 is an integer of 0 to 10;

In the general formula (4), R ⁴¹ represents a monovalent group, and R ⁴¹ is the same as R ¹¹ in the general formula (1).

In the formula 4, R ⁴² represents an alkylene group. The number of carbon atoms of the alkylene group is preferably 10 or less, more preferably 6 or less, still more preferably 3 or less, and the lower limit may be 1 or more. Among them, a methylene group and a dimethylethylene group are preferable from the viewpoint of obtaining a desired effect of the present invention remarkably.

In the general formula (4), n4 represents an integer of 0 to 10, and n4 is equal to n3 in the general formula (3).

The phenylene group in the formula (4) is preferably bonded to the alkylene group represented by two R &lt; ⁴² &gt; at the 1-position and the 4-position.

The aromatic hydrocarbon resin represented by the general formula (4) is preferably an aromatic hydrocarbon resin represented by the following general formula (5).

In Formula 5,

R ⁵¹ each independently represents a monovalent group,

R ⁵² each independently represents an alkylene group,

n5 is an integer of 0 to 10;

In the general formula (5), R ⁵¹ represents a monovalent group, and R ⁵¹ is the same as R ¹¹ in the general formula (1).

In formula (5), R ⁵² represents an alkylene group. R ⁵² is the same as R ⁴² in the formula (4).

In the general formula (5), n5 represents an integer of 0 to 10, and n5 is equal to n3 in the general formula (3).

Among them, the component (A) is preferably an aromatic hydrocarbon resin represented by the following formula (6).

[Chemical Formula 6]

In Formula 6,

R ⁶¹ each independently represents a monovalent group,

n6 is an integer of 0 to 10;

In the general formula (6), R ⁶¹ represents a monovalent group, and R ⁶¹ is the same as R ¹¹ in the general formula (1).

In the formula (6), n6 represents an integer of 0 to 10, and n6 is the same as n3 in the formula (3).

Examples of commercially available products of the component (A) include "ESN375", "SN395", "HP4032", "HP4032D", "HP4032SS", "HP4032H", "HP4700 , &Quot; HP4710 &quot;, and &quot; NC3500 &quot; manufactured by Nihon Kayaku Co.,

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

When the group containing an oxygen atom bonded to the aromatic ring of the component (A) contains an epoxy group, the epoxy equivalent of the component (A) is preferably from 50 to 5,000 g / eq., more preferably 50 to 3,000 g / eq., more preferably 80 to 2,000 g / eq., even more preferably 90 to 1,000 g / eq. The epoxy equivalent is the mass of the resin containing one equivalent of epoxy group. This epoxy equivalent can be measured according to JIS K 7236.

When the group containing an oxygen atom bonded to the aromatic ring of the component (A) contains a hydroxyl group, the hydroxyl equivalent of the component (A) is preferably from the viewpoint of increasing the crosslinking density of the insulating layer as the cured product of the resin composition layer, From the viewpoint of achieving a desired effect of the present invention, preferably 50 g / eq. Or more, more preferably 60 g / eq. More preferably 70 g / eq. And more preferably 250 g / eq. More preferably 150 g / eq. Particularly preferably 120 g / eq. Or less. The hydroxyl equivalent is the mass of the resin containing one equivalent of hydroxyl groups.

When the group containing an oxygen atom bonded to the aromatic ring of the component (A) contains a hydroxyl group and the number of epoxy groups of the epoxy resin (C) is 1, the oxygen atom bonded to the aromatic ring of the component (A) Is preferably 1 or more, more preferably 5 or more, further preferably 10 or more, preferably 30 or less, still more preferably 30 or less, still more preferably 30 or less, Is 25 or less, more preferably 20 or less. Here, the "epoxy group number of the epoxy resin (C)" is a value obtained by dividing the mass of the nonvolatile component of the component (C) present in the resin composition by the epoxy equivalent. The term "a group containing an oxygen atom bonded to an aromatic ring of the component (A)" refers to a group containing an oxygen atom that bonds an aromatic ring to the aromatic ring, And the value divided by the equivalent of the group.

The content of the component (A) is preferably 0.5% by mass or more, more preferably 0.8% by mass or more, more preferably 0.8% by mass or more, More preferably not less than 1% by mass, preferably not more than 15% by mass, more preferably not more than 10% by mass, further preferably not more than 8% by mass or not more than 5% by mass.

In the present invention, the content of each component in the resin composition is a value obtained by assuming that the nonvolatile component in the resin composition is 100% by mass, unless otherwise specified.

The content of the component (A) is preferably from 2% by mass, more preferably from 2% by mass, based on 100% by mass of the total content of the component (A) and the epoxy resin (C) described below from the viewpoint of obtaining a cured product having superior smear- More preferably 5 mass% or more, further preferably 15 mass% or more, preferably 50 mass% or less, more preferably 40 mass% or less, still more preferably 30 mass% or less.

<(B) Active ester-based curing agent>

The resin composition contains (B) an active ester-based curing agent. When the active ester type curing agent is used, the dielectric tangent can be generally lowered and the smear removal property is lowered. However, since the resin composition of the present invention contains the component (A), it becomes possible to obtain a resin composition capable of lowering the dielectric loss tangent and obtaining a cured product excellent in smear removal property.

Examples of the active ester curing agent (B) generally include ester groups having high reactivity, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, Are preferably used. The active ester curing agent is preferably obtained by a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. From the viewpoint of heat resistance improvement, an active ester type curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester type curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid and the like. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o- Cresol, catechol, alpha -naphthol, beta -naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, Trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglucine, benzene triol, dicyclopentadiene type diphenol compounds, phenol novolak, and the like. Here, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol in one dicyclopentadiene molecule.

Specifically, there may be mentioned a dicyclopentadiene type active ester type curing agent, an active ester type curing agent containing a naphthalene structure, an active ester type curing agent containing an acetylated phenol novolac, an active ester type Among them, an active ester type curing agent containing a naphthalene structure and a dicyclopentadiene type active ester type curing agent are more preferable, and a dicyclopentadiene type active ester type curing agent is more preferable. As the dicyclopentadiene type active ester type curing agent, an active ester type curing agent containing a dicyclopentadiene type diphenol structure is preferable. The "dicyclopentadiene type diphenol structure" refers to a divalent structural unit comprising phenylene-dicyclopentylene-phenylene.

(EXB9451), EXB9460, EXB9460S, HPC-8000-65T, HPC-8000-65T and HPC-8000-65T as active ester curing agents containing a dicyclopentadiene type diphenol structure as commercially available products of the active ester curing agent (B) EXB8150-60T "," EXB9416-70BK "(manufactured by DIC) as an active ester curing agent containing a naphthalene structure, acetylated products of phenol novolak Quot; DC808 &quot; (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester-based curing agent and YLH1026 (manufactured by Mitsubishi Chemical Corp.) as an active ester-based curing agent containing a benzoylate of phenol novolak, , "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.), "YLH1030" (manufactured by Mitsubishi Chemical Co., Ltd.) and "YLH1048" (manufactured by Mitsubishi Chemical Corporation) were used as the ester- based curing agent, "DC808" Mitsu When the like Chemical Company).

(A) and (C): the total number of epoxy groups of the components (A) and (C): the total number of reactors of the active ester-based curing agent] , Preferably in the range of 1: 0.01 to 1: 5, more preferably 1: 0.05 to 1: 2, and even more preferably 1: 0.1 to 1: 1.8. Here, the reactive ester curing agent is an active ester group. The total number of epoxy groups in the components (A) and (C) means the value obtained by dividing the solid mass of each component by the epoxy equivalent. The total number of reactors of the active ester type curing agent and the total number of active ester type curing agents The value obtained by dividing the mass of the solid component by the equivalent of the reactor in terms of all the active ester-based curing agents. By setting the ratio of the epoxy resin and the active ester type curing agent to this range, the heat resistance of the cured product of the resin composition is further improved.

The content of the active ester curing agent (B) in the resin composition is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, based on 100% by mass of the nonvolatile component in the resin composition to be. The upper limit is preferably 30 mass% or less, more preferably 20 mass% or less, further preferably 15 mass% or less. By making the content of the component (B) fall within this range, it becomes possible to obtain a cured product having excellent smear removal properties.

&Lt; (C) Epoxy resin >

The resin composition may contain (C) an epoxy resin. However, the component (C) is not limited to the component (A).

Examples of the epoxy resin (C) include epoxy resins such as bicalcylenol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, dicyclopentadiene type epoxy resins, A phenol type epoxy resin, a naphthol novolak type epoxy resin, a phenol novolak type epoxy resin, a tert-butyl catechol type epoxy resin, a naphthalene type epoxy resin, a naphthol type epoxy resin, an anthracene type epoxy resin, , Glycidyl ester type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring containing epoxy resin, Cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, naphthylene ether type epoxy resin Trimethylol type epoxy resin, tetraphenylethan type epoxy resin, and the like. One type of epoxy resin may be used alone, or two or more types may be used in combination.

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

The epoxy resin includes epoxy resin (hereinafter sometimes referred to as &quot; liquid epoxy resin &quot;) which is liquid at a temperature of 20 占 폚, epoxy resin which is solid at 20 占 폚 . The resin composition may contain only liquid epoxy resin (C) as the epoxy resin, or may contain only solid epoxy resin, but it is preferable that the resin composition contains a combination of a liquid epoxy resin and a solid epoxy resin. (C) When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, the flexibility of the resin composition layer can be improved or the breaking strength of the cured product of the resin composition layer can be improved.

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

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

Specific examples of the liquid epoxy resin include "828US", "jER828EL", "825", "Epikote 828EL" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "JER807" and "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "JER152" (phenol novolak type epoxy resin) manufactured by Mitsubishi Chemical Corporation; 630 &quot;, &quot; 630LSD &quot; (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; ZX1059 &quot; (a mixture of a bisphenol A type epoxy resin and a bisphenol F type epoxy resin) manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd.; EX-721 &quot; (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Corporation; "SEROCIDE 2021P" (an alicyclic epoxy resin having an ester skeleton) manufactured by DICEL Corporation; &Quot; PB-3600 &quot; (epoxy resin having a butadiene structure) manufactured by Daicel Company; ZX1658 &quot; and &quot; ZX1658GS &quot; (liquid 1,4-glycidyl cyclohexane type epoxy resin) manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., and the like. These may be used singly or in combination of two or more.

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

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

Specific examples of the solid epoxy resin include &quot; N-690 &quot; (cresol novolak type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolak type epoxy resin) manufactured by DIC Corporation; "HP-7200", "HP-7200HH" and "HP-7200H" (dicyclopentadiene type epoxy resin) manufactured by DIC Corporation; "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin) manufactured by DIC Corporation; EPPN-502H &quot; (trisphenol type epoxy resin) manufactured by Nihon Kayakusa; NC7000L &quot; (naphthol novolak type epoxy resin) manufactured by Nihon Kayakusa; "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin) manufactured by Nihon Kayakusa; "ESN475V" (naphthol type epoxy resin) manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd.; "ESN485" (naphthol novolak type epoxy resin) manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd.; "YX4000H", "YX4000", and "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation; &Quot; YX4000HK &quot; (biquileneol type epoxy resin) manufactured by Mitsubishi Chemical Corporation; &Quot; YX8800 &quot; (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd.; "YL7760" (Bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; &Quot; jER1010 &quot; (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; And &quot; jER1031S &quot; (tetraphenyl ethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation. These may be used singly or in combination of two or more.

(C) When a liquid epoxy resin and a solid epoxy resin are used in combination as an epoxy resin, the ratio of these amounts (liquid epoxy resin: solid epoxy resin) is preferably 1: 1 to 1:20, more preferably 1: 1 to 1:15, particularly preferably 1: 1 to 1:10. The amount ratio of the liquid epoxy resin and the solid epoxy resin falls within this range, and the desired effect of the present invention can be obtained remarkably. Further, usually, when used in the form of a resin sheet, appropriate tackiness is caused. Further, in general, when used in the form of a resin sheet, sufficient flexibility is obtained and handling is improved. Usually, a cured product having sufficient breaking strength can be obtained.

The epoxy equivalent of the epoxy resin (C) is preferably 50 to 5,000 g / eq., More preferably 50 to 3,000 g / eq., Further preferably 80 to 2,000 g / eq. 110 to 1,000 g / eq. With such a range, the cross-linking density of the cured product of the resin composition layer becomes sufficient, and an insulating layer having a small surface roughness may be caused. The epoxy equivalent is the mass of the resin containing one equivalent of epoxy group. This epoxy equivalent can be measured according to JIS K7236.

The weight average molecular weight (Mw) of the epoxy resin (C) is preferably 100 to 5,000, more preferably 250 to 3,000, and still more preferably 400 to 1,500 from the viewpoint of obtaining the desired effect of the present invention.

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

In the case where the resin composition contains the epoxy resin (C), the content of the epoxy resin (C) is preferably in the range of 100 mass% or less in terms of the nonvolatile component in the resin composition from the viewpoint of obtaining an insulating layer showing good mechanical strength and insulation reliability , Preferably not less than 1% by mass, more preferably not less than 3% by mass, and further preferably not less than 5% by mass. The upper limit of the content of the epoxy resin is preferably 30% by mass or less, more preferably 25% by mass or less, particularly preferably 20% by mass or less from the viewpoint of obtaining the desired effect of the present invention remarkably.

<(D) Inorganic filler>

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

Examples of the commercially available inorganic filler (D) include "SP60-05" and "SP507-05" manufactured by Shinnitetsu Sumikin Materials Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE" and "YA010C" manufactured by Adomatex Co., "UFP-30" manufactured by Denka Corporation; "Silphil NSS-3N", "Silphil NSS-4N" and "Silpil NSS-5N" manufactured by Tokuyama Corporation; "SC2500SQ", "SO-C4", "SO-C2" and "SO-C1" manufactured by Adomatex Co., Ltd.

The average particle diameter of the inorganic filler (D) is preferably at least 0.01 탆, more preferably at least 0.05 탆, particularly preferably at least 0.1 탆, from the viewpoint of obtaining the desired effect of the present invention remarkably, 5 mu m or less, more preferably 2 mu m or less, and further preferably 1 mu m or less.

The average particle diameter of the inorganic filler (D) can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, the particle diameter distribution of the inorganic filler can be measured by using a laser diffraction scattering particle diameter distribution measuring apparatus, and the median diameter of the inorganic filler is determined based on the volume, and the average particle diameter can be measured. As a measurement sample, 100 mg of inorganic filler, 0.1 g of dispersant ("SN9228" manufactured by Sanofuco) and 10 g of methyl ethyl ketone were placed in a vial bottle and dispersed by ultrasonic wave for 20 minutes. The measurement sample was measured for particle diameter distribution in a batch cell system using a laser diffraction particle diameter distribution analyzer (&quot; SALD-2200 &quot; manufactured by Shimadzu Corporation), and the average particle diameter as a median diameter was calculated.

The specific surface area of the inorganic filler (D) is preferably 1 m 2 / g or more, more preferably 2 m 2 / g or more, particularly preferably 5 m 2 / g or more, from the viewpoint of facilitating the control of the via- Lt; 2 &gt; / g or more. The upper limit is not particularly limited, but is preferably 60 m 2 / g or less, 50 m 2 / g or less, or 40 m 2 / g or less. The specific surface area of the inorganic filler can be measured by the BET method.

The inorganic filler (D) is preferably treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Examples of the surface treatment agent include a fluorine-containing silane coupling agent, an aminosilane coupling agent, an epoxy silane coupling agent, a mercaptosilane coupling agent, a silane coupling agent, an alkoxysilane, an organosilazane compound, LINGER, and the like. The surface treatment agent may be used singly or in combination of two or more kinds.

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

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

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

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

When the resin composition (D) contains an inorganic filler, the content of the inorganic filler (D) is preferably 50 mass% or more, more preferably 50 mass% or less, More preferably 60 mass% or more, further preferably 65 mass% or more, preferably 90 mass% or less, more preferably 85 mass% or less, further preferably 80 mass% or less.

<(E) Curing agent>

The resin composition may contain (E) a curing agent. However, the active ester-based curing agent (B) is not included in the curing agent (E). Examples of the curing agent (E) include a phenol-based curing agent, a naphthol-based curing agent, a benzoxazine-based curing agent, a cyanate ester-based curing agent, and a carbodiimide-based curing agent. Among them, from the viewpoint of improving the insulation reliability, the (E) curing agent is preferably at least one of a phenol-based curing agent, a naphthol-based curing agent, a cyanate ester-based curing agent, and a carbodiimide-based curing agent, Or more. The curing agent may be used singly or in combination of two or more kinds.

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

Specific examples of the phenol-based curing agent and naphthol-based curing agent include "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Showa Kasei Co., Ltd., "NHN" SN375 "," SN495 "," SN-495V "," SN375 "," SN395 "," SN375 "," TD-2090 "," LA-7052 "," LA-7054 "," LA-1356 "," LA-3018-50P "and" EXB-9500 "manufactured by DIC Corporation.

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

Examples of the cyanate ester curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4'- Dimethylphenyl cyanate), 4,4'-ethylidenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1- Cyanate phenylmethane), bis (4-cyanate-3,5-dimethylphenyl) methane, 1,3-bis Bifunctional cyanate resins derived from phenolic novolacs and cresol novolacs such as bis (4-cyanophenyl) thioether and bis (4-cyanate phenyl) ether, and polyfunctional cyanate resins derived from these cyanate resins, And prepolymers. Specific examples of the cyanate ester curing agent include "PT30" and "PT60" (phenol novolac type polyfunctional cyanate ester resin), "ULL-950S" (multifunctional cyanate ester resin), "BA230 , &Quot; BA230S75 &quot; (a prepolymer obtained by trimerizing a part or all of bisphenol A dicyanate to form a trimer), and the like.

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

When the resin composition contains (E) a curing agent, the ratio of the amounts of the components (A) and (C) and the curing agent (E) is such that the total number of epoxy groups of the components (A) and Is preferably in the range of 1: 0.01 to 1: 2, more preferably 1: 0.01 to 1: 1, further preferably 1: 0.03 to 1: 0.5. Here, the reactive group of the curing agent is an active hydroxyl group or the like, which differs depending on the kind of the curing agent. The total number of reactors of the curing agent, and the value obtained by dividing the solid content of each curing agent by the equivalent of the reactor, in terms of all the curing agents. By setting the ratio of the components (A) and (C) to the curing agent within this range, the heat resistance of the cured product of the resin composition is further improved.

When the resin composition contains (B) the active ester type curing agent and (E) the curing agent, the ratio of the amounts of the components (A) and (C), (B) the active ester type curing agent, and (E) Is preferably in the range of 1: 0.01 to 1: 5, more preferably in the range of 1: 0.05 to 1: 5 in terms of the ratio of [the total number of epoxy groups of the component (B) and the component (E) 2, more preferably from 1: 0.1 to 1: 1. By setting these proportions to such a range, the heat resistance of the cured product of the resin composition is further improved.

When the resin composition contains (E) a curing agent, the content of the (E) curing agent is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, Or more, and more preferably 0.5 mass% or more. The upper limit is preferably 5 mass% or less, more preferably 3 mass% or less, further preferably 1 mass% or less. When the content of the (E) curing agent is within this range, the heat resistance of the cured product of the resin composition is further improved.

&Lt; (F) Thermoplastic resin >

The resin composition may contain (F) a thermoplastic resin. Examples of the thermoplastic resin as the component (F) include phenoxy resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyimide resins, polyamideimide resins, polyetherimide resins, polysulfone resins, Resins, polyphenylene ether resins, polycarbonate resins, polyether ether ketone resins, and polyester resins. Of these, a phenoxy resin is preferable from the standpoint of obtaining a desired effect of the present invention remarkably and from the viewpoint of obtaining an insulating layer having a small surface roughness and excellent adhesion to a conductor layer. The thermoplastic resin may be used singly or in combination of two or more kinds.

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

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

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

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

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

Specific examples of the polyethersulfone resin include "PES 5003P" manufactured by Sumitomo Chemical Co., Ltd., and the like.

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

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

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

In the case where the resin composition contains (F) a thermoplastic resin, the content of the thermoplastic resin (F) is preferably in the range of from 100% by mass to 100% by mass in the resin composition from the viewpoint of obtaining the desired effect of the present invention Is preferably 0.1 mass% or more, more preferably 0.2 mass% or more, further preferably 0.3 mass% or more, preferably 1.5 mass% or less, more preferably 1 mass% or less, further preferably 0.5 mass% to be.

<(G) Curing accelerator>

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

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

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

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

As the imidazole-based curing accelerator, commercially available products may be used, and for example, "P200-H50" manufactured by Mitsubishi Chemical Co., Ltd. and the like can be mentioned.

Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, Guanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] deca-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0 ] Deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1 , 1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide and 1- (o-tolyl) , 1,5,7-triazabicyclo [4.4.0] deca-5-ene.

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

When the resin composition contains a curing accelerator (G), the content of the curing accelerator (G) is preferably from 100% by mass to 100% by mass, Is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, further preferably 0.1 mass% or more, preferably 3 mass% or less, more preferably 2 mass% or less, further preferably 1.5 mass% to be.

&Lt; (H) Optional additives >

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

&Lt; Physical properties and uses of resin composition >

The cured product obtained by thermosetting the resin composition at 100 占 폚 for 30 minutes and then at 170 占 폚 for 30 minutes generally exhibits excellent smear removal properties. Therefore, even when a via hole is formed in the cured product, the maximum smear length of the via hole bottom portion is less than 5 탆. The smear removability can be measured by the method described in the following examples.

The cured product obtained by thermosetting the resin composition at 200 캜 for 90 minutes exhibits a low dielectric tangent. Thus, dielectric tangent results in an insulating layer with low electrical conductivity. The dielectric loss tangent is preferably 0.01 or less, more preferably 0.008 or less, and still more preferably 0.005 or less. The lower limit is not particularly limited, but may be 0.0001 or more. The dielectric loss tangent can be measured by the method described in the following Examples.

The resin composition of the present invention may result in an insulating layer having a low dielectric tangent and an excellent smear removal property. Therefore, the resin composition of the present invention can be suitably used as a resin composition (a resin composition for an insulating layer of a multilayer printed circuit board) for forming an insulating layer of a multilayered printed circuit board, and a resin composition for forming an interlayer insulating layer of a printed wiring board (A resin composition for an interlaminar insulating layer of a printed wiring board). Further, the resin composition of the present invention can be suitably used even in the case where the printed wiring board is a component built-in circuit board, because it results in an insulating layer having a good part filling property.

Particularly, since the resin composition of the present invention has a low dielectric tangent and can lead to an insulating layer excellent in smear removal property, it becomes possible to form an insulating layer having a small diameter of a via hole. Therefore, the resin composition is suitable as a resin composition (a resin composition for forming an insulating layer having a via hole) for forming an insulating layer having via holes, and among these, a resin for forming an insulating layer having a via- A composition, a resin composition for forming an insulating layer having a via hole having a thickness (mu m) of an insulating layer and an aspect ratio (thickness of an insulating layer / top diameter) of a top diameter (mu m) of 0.5 or more. Here, the term &quot; top diameter &quot; refers to the maximum diameter of the opening formed on the opposite side of the via hole to the substrate when a via hole is formed in the insulating layer on the substrate, and the &quot; thickness of the insulating layer &quot; That is, the depth of the via.

The aspect ratio (insulating layer thickness / top diameter) of the insulating layer thickness (占 퐉) and the top diameter (占 퐉) is preferably 0.5 or more, more preferably 0.6 or more, Preferably 0.7 or more, preferably 3 or less, more preferably 2 or less, further preferably 1 or less.

[Resin sheet]

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

The thickness of the resin composition layer is preferably 40 占 퐉 or less, more preferably 35 占 퐉 or less, further preferably 25 占 퐉 or less from the viewpoint of thinning the printed wiring board and providing a cured product having excellent insulating properties even in the form of a thin film , And 20 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but may be usually 3 占 퐉 or more, 5 占 퐉 or more, 7 占 퐉 or more, or the like.

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

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

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

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

As the support, a support having a release layer having a release layer on the surface to be bonded to the resin composition layer may be used. Examples of the release agent used for the release layer of the release layer-adhered support include at least one release agent selected from the group consisting of an alkyd resin, a polyolefin resin, a urethane resin, and a silicone resin. The release layer-adhered support may be a commercially available product, and is, for example, a PET film having a release layer containing an alkyd resin-based release agent as a main component. SK-1 &quot;, &quot; AL-5 &quot;, &quot; AL-7 &quot;, Lumirra T60 manufactured by Toray Industries, Inc., Purex manufactured by Teijin Co., .

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

In one embodiment, the resin sheet may further include other layers as required. Examples of the other layer include a protective film based on a support provided on a surface of the resin composition layer not bonded to a support (that is, a surface opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 to 40 탆. By laminating a protective film, adhesion and scratches of dust or the like to the surface of the resin composition layer can be suppressed.

The resin sheet can be produced, for example, by preparing a resin varnish obtained by dissolving a resin composition in an organic solvent, coating the resin varnish on a support using a die coater or the like, and drying the resin varnish again to form a resin composition layer .

Examples of the organic solvent include 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; Carbitol such as cellosolve and butyl carbitol; Aromatic hydrocarbons such as toluene and xylene; And amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. The organic solvent may be used singly or in combination of two or more kinds.

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

The resin sheet can be rolled up and stored. When the resin sheet has a protective film, it can be used by peeling the protective film.

[Printed circuit board]

The printed wiring board of the present invention includes an insulating layer formed by a cured product of the resin composition of the present invention.

The printed wiring board can be produced, for example, by a method including the steps (I) and (II) using the above resin sheet.

(I) a step of laminating a resin composition layer of a resin sheet to be laminated on an inner layer substrate on an inner layer substrate

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

The &quot; inner layer substrate &quot; used in the step (I) is a member which becomes a substrate of a printed wiring board, and examples thereof include glass epoxy substrate, metal substrate, polyester substrate, polyimide substrate, BT resin substrate, Ether substrates and the like. Further, the substrate may have a conductor layer on one side or both sides thereof, and the conductor layer may be patterned. An inner layer substrate on which a conductor layer (circuit) is formed on one side or both sides of the substrate is sometimes referred to as an &quot; inner layer circuit substrate &quot;. Further, in manufacturing a printed wiring board, an intermediate product in which an insulating layer and / or a conductor layer is to be further formed is also included in the &quot; inner layer substrate &quot; When the printed wiring board is a component built-in circuit board, an inner-layer board containing components can be used.

The lamination of the inner layer substrate and the resin sheet can be performed, for example, by thermocompression bonding the resin sheet to the inner layer substrate on the support side. Examples of the member for heating and pressing the resin sheet to the inner layer substrate (hereinafter, also referred to as &quot; hot pressing member &quot;) include a heated metal plate (SUS hard plate) or a metal roll (SUS roll). It is also preferable to press the heat-press member through an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently follow the surface unevenness of the inner layer substrate without directly pressing the heat-press member to the resin sheet.

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

The lamination can be performed by a commercial vacuum laminator. As a commercially available vacuum laminator, for example, a vacuum pressurized laminator manufactured by Meikisha Sakusho Co., Ltd., a vacuum applicator manufactured by Nikko MATERIALS Co., Ltd., and a batch vacuum pressure laminator are listed.

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

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

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

The thermosetting conditions of the resin composition layer are not particularly limited, and conditions that are generally employed when forming the insulating layer of the printed wiring board may be used.

For example, the thermosetting condition of the resin composition layer varies depending on the kind of the resin composition and the like, but the curing temperature is preferably 120 to 240 캜, more preferably 150 to 220 캜, still more preferably 170 to 200 / RTI &gt; The curing time is preferably 5 to 120 minutes, more preferably 10 to 100 minutes, and further preferably 15 to 90 minutes.

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

In the production of a printed wiring board, (III) a step of piercing the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer may be further performed. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art, which are used in the production of printed wiring boards. When the support is removed after the step (II), the removal of the support is carried out between the step (II) and the step (III), between the step (III) and the step (IV) ). If necessary, the multilayer printed wiring board may be formed by repeating the formation of the insulating layer and the conductor layer in the process (II) and the process (V).

The step (III) is a step of perforating the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. The step (III) may be carried out using, for example, a drill, a laser or a plasma, depending on the composition of the resin composition used for forming the insulating layer. The dimensions and shape of the holes may be suitably determined in accordance with the design of the printed wiring board.

The top diameter of the via hole is preferably 70 占 퐉 or less, more preferably 60 占 퐉 or less, further preferably 55 占 퐉 or less, or 35 占 퐉 or less, from the viewpoint of miniaturization and high performance of electronic equipment. The lower limit is not particularly limited, but may be 10 탆 or more. The top diameter of the via hole can be measured by using, for example, SEM.

Step (IV) is a step of roughening the insulating layer. Usually, smear removal is also performed in this step (IV). The procedure and condition of the roughening treatment are not particularly limited, and a well-known procedure and conditions usually used in forming the insulating layer of the printed wiring board can be adopted. For example, swelling treatment with a swelling liquid, coarsening treatment with an oxidizing agent, and neutralization treatment with a neutralizing liquid can be carried out in this order to roughen the insulating layer. The swelling liquid to be used for the harmonic treatment is not particularly limited, but examples thereof include an alkaline solution and a surfactant solution, preferably an alkaline solution. More preferably, the alkaline solution is a sodium hydroxide solution or a potassium hydroxide solution. Examples of commercially available swelling liquids include Swelling Dip Sicergans P manufactured by Atotech Japan Co., Ltd., Swelling Dip Sekurigans SBU, and the like. The swelling treatment with the swelling liquid is not particularly limited, and can be performed, for example, by immersing the insulating layer in a swelling liquid at 30 to 90 캜 for 1 to 20 minutes. From the standpoint of suppressing the swelling of the resin in the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in the swelling liquid at 40 to 80 DEG C for 5 to 15 minutes. The oxidizing agent used for the harmonic treatment is not particularly limited, and for example, an alkaline permanganic acid solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide may be mentioned. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated to 60 to 80 캜 for 10 to 30 minutes. The concentration of the permanganate in the alkaline permanganic acid solution is preferably 5 to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as "Concentrate Compact CP" manufactured by Atotech Japan Co., Ltd., "Dozing Solution · Sicuregan P", and the like. An acidic aqueous solution is preferable as a neutralizing solution used for harmonization, and a commercially available product includes, for example, "Reduction Solution · Sucuregent P" manufactured by Atotech Japan Co., Ltd. The treatment with the neutralizing liquid can be performed by immersing the treated surface subjected to the roughening treatment with the oxidizing agent in a neutralizing solution at 30 to 80 캜 for 5 to 30 minutes. From the standpoint of workability and the like, it is preferable to immerse the object subjected to the roughening treatment with an oxidizing agent in a neutralizing solution at 40 to 70 캜 for 5 to 20 minutes.

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

Step (V) is a step of forming a conductor layer, and a conductor layer is formed on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer contains at least one metal selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, do. The conductor layer may be a single metal layer or an alloy layer. Examples of the alloy layer include alloys of two or more metals (for example, nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy) May be used. Among them, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper single metal layer or nickel-chromium alloy, copper-nickel alloy, An alloy layer of a copper-titanium alloy is preferable and an alloy layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper alloy layer or nickel-chromium alloy is more preferable, Do.

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 stacked. When the conductor layer has a multilayer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of a nickel-chromium alloy.

The thickness of the conductor layer varies depending on the design of a desired printed wiring board, but is generally 3 to 35 占 퐉, preferably 5 to 30 占 퐉.

In one embodiment, the conductor layer may be formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating on the surface of an insulating layer by a conventionally known technique such as a semi-custom method or a pull-on-fill method. In view of simplicity of manufacture, It is preferable to form it by a customary method. Hereinafter, an example in which the conductor layer is formed by the semi-

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Subsequently, a mask pattern is formed on the formed plating seed layer to expose a part of the plating seed layer corresponding to the desired wiring pattern. A metal layer is formed on the exposed plating seed layer by electrolytic plating, and then the mask pattern is removed. Thereafter, an unnecessary plating seed layer is removed by etching or the like, and a conductor layer having a desired wiring pattern can be formed.

The resin sheet of the present invention can be suitably used even in the case where the printed wiring board is a component built-in circuit board, because the resin sheet results in an insulating layer with good part embedding property. The component built-in circuit board can be manufactured by a known manufacturing method.

The printed wiring board manufactured using the resin sheet of the present invention may be provided with an insulating layer which is a cured product of the resin composition layer of the resin sheet and a buried wiring layer embedded in the insulating layer.

[Semiconductor device]

The semiconductor device of the present invention includes the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured by using the printed wiring board of the present invention.

Examples of the semiconductor device include various semiconductor devices provided in the above products (such as a computer, a mobile phone, a digital camera and a television) and a vehicle (such as a motorcycle, a car, a train, a ship and an aircraft) have.

The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) to a conductive portion of a printed wiring board. The &quot; conduction point &quot; is a &quot; point at which the signal is transmitted to the printed wiring board &quot;, and may be a surface or a buried point. The semiconductor chip is not particularly limited as long as it is the above-described circuit element made of a semiconductor material.

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

[Example]

Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to the following examples. In the following description, &quot; part &quot; and &quot;% &quot; representing the amount means &quot; part by mass &quot; and &quot;% by mass &quot;, respectively, unless otherwise specified. In addition, the operations described below were performed under an ambient temperature and normal pressure condition unless otherwise specified.

[Example 1]

10 parts of a bisphenol-type epoxy resin ("ZX1059" manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., a 1: 1 mixture of bisphenol A and bisphenol F type, epoxy equivalent 169) and 10 parts of a naphthol type epoxy resin &Quot; ESN475V &quot;, epoxy equivalent of about 330) was dissolved by heating in 40 parts of solvent naphtha with stirring. This was cooled to room temperature to prepare a dissolution composition of the epoxy resin (X).

Further, 10 parts of an aromatic hydrocarbon resin ("ESN375", manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., epoxy equivalent: about 171) having the structure shown below was dissolved by heating in 10 parts of MEK while stirring and further cooled to room temperature to obtain an aromatic hydrocarbon resin (Y) was prepared.

(n is an integer of 1 to 10)

5 parts of a phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Co., Ltd., a 1: 1 solution of MEK and cyclohexanone in a solid content of 30 mass%), a triazine skeleton and a novolak structure were added to the solution composition of the epoxy resin , 5 parts of a phenol-based curing agent ("LA-3018-50P" manufactured by DIC Corporation, active agent equivalent weight of about 151, 50% solids content of a 2-methoxypropanol solution), an active ester type curing agent ("HPC-8000-65T" 5 parts of a curing accelerator (1-benzyl-2-phenylimidazole (1B2PZ), 10% by mass of solid content of MEK solution), 50 parts of an amine alkoxysilane compound , 220 parts of spherical silica (average particle diameter 0.77 mu m, &quot; SO-C2 &quot; manufactured by Adomex Co., Ltd.) surface-treated with a surfactant (KBM573, manufactured by Shin-Etsu Chemical Co., Ltd.) and 20 parts of a solution of an aromatic hydrocarbon resin And uniformly dispersed in a high-speed rotary mixer to prepare a resin varnish.

As a support, a polyethylene terephthalate film ("AL5" manufactured by Lintec Corp., thickness 38 μm, PET film) having a release layer was prepared. On the release layer of the support, the resin varnish was uniformly applied so that the thickness of the resin composition layer after drying was 15 占 퐉. Thereafter, the resin varnish was dried at 80 to 100 캜 (average 90 캜) for 3 minutes to prepare a resin sheet including a support and a resin composition layer.

[Example 2]

50 parts of an active ester type curing agent ("HPC-8000-65T" manufactured by DIC Corporation, active equivalent weight of about 223, and a solid content of 65% by mass) in Example 1 was mixed with an active ester type curing agent ("EXB8000L-65TM , An activating group equivalent of 220, and a solid content of 65% toluene-MEK mixed solution). A resin varnish and a resin sheet were produced in the same manner as in Example 1 except for the above.

[Example 3]

50 parts of an active ester type curing agent ("HPC-8000-65T" manufactured by DIC Corporation, active equivalent weight of about 223 and a solid content of 65% by weight) in Example 1 was mixed with an active ester type curing agent ("EXB8150-60T Quot ;, active agent equivalent 230, 60% solids in toluene solution). A resin varnish and a resin sheet were produced in the same manner as in Example 1 except for the above.

[Example 4]

10 parts of a bisphenol-type epoxy resin ("ZX1059" manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., a 1: 1 mixture of bisphenol A and bisphenol F type, epoxy equivalent 169) and 10 parts of a naphthol type epoxy resin &Quot; ESN475V &quot;, epoxy equivalent of about 330) were dissolved by heating in 40 parts of solvent naphtha with stirring. This was cooled to room temperature to prepare a dissolution composition of the epoxy resin (X2).

Further, 20 parts of an aromatic hydrocarbon resin ("ESN375" manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., epoxy equivalent: 171) was dissolved by heating in 20 parts of MEK while stirring, and then cooled to room temperature to obtain a solution of the aromatic hydrocarbon resin Was prepared.

5 parts of a phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Co., Ltd., a 1: 1 solution of MEK and cyclohexanone in a solid content of 30 mass%), an active ester type curing agent (manufactured by DIC Corporation) , 5 parts of a curing accelerator (1-benzyl-2-phenylimidazole (1B2PZ), 10% by mass of solid content of a MEK solution), 80 parts of an amine-based , 250 parts of spherical silica (average particle diameter of 0.77 mu m, "SO-C2" manufactured by Adomex Co., Ltd.) surface-treated with an alkoxysilane compound (KBM573 manufactured by Shin-Etsu Chemical Co., Ltd.) and a solution of an aromatic hydrocarbon resin Were mixed and uniformly dispersed in a high-speed rotary mixer to prepare a resin varnish. A resin sheet was prepared in the same manner as in Example 1.

[Example 5]

In Example 3,

1) The amount of 20 parts of an aromatic hydrocarbon resin ("ESN375" manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., epoxy equivalent: about 171) was changed from 20 parts to 5 parts,

2) The amount of naphthol-type epoxy resin ("ESN475V" manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., epoxy equivalent: about 330) was changed from 30 parts to 40 parts,

3) The amount of spherical silica (average particle diameter 0.77 mu m, "SO-C2" manufactured by Adomex Co., Ltd.) surface-treated with an amine alkoxysilane compound (KBM573 manufactured by Shin-Etsu Chemical Co., Ltd.) was changed from 220 parts to 230 parts Change.

A resin varnish and a resin sheet were produced in the same manner as in Example 1 except for the above.

[Example 6]

10 parts of a bisphenol-type epoxy resin ("ZX1059" manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., a 1: 1 mixture of bisphenol A and bisphenol F type, epoxy equivalent 169) and 10 parts of a naphthol type epoxy resin &Quot; ESN475V &quot;, epoxy equivalent: about 330) were dissolved by heating in 40 parts of solvent naphtha with stirring. This was cooled to room temperature to prepare a dissolution composition of the epoxy resin (X3).

Further, 3 parts of an aromatic hydrocarbon resin ("SN395-50M" manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., active group equivalent 107, used as a solution of MEK having a solid content of 50%) shown below and 3 parts of an aromatic hydrocarbon resin (Shinnitetsu Sumikin Kaga 5 parts of epoxy resin ("ESN375" manufactured by Kusa Co., Ltd., epoxy equivalent: 171) were dissolved by heating in 10 parts of MEK with stirring, and then cooled to room temperature to prepare a solution of aromatic hydrocarbon resin (Y3).

(n is an integer of 1 to 10)

5 parts of a phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Co., Ltd., a 1: 1 solution of MEK and cyclohexanone in a solid content of 30 mass%), a 7-triazine skeleton and a novolak structure , 2 parts of a phenolic curing agent ("LA-3018-50P" manufactured by DIC Corporation, active agent equivalent weight of about 151, 50% of solid content of 2-methoxypropanol solution) 5 parts of a curing accelerator (1-benzyl-2-phenylimidazole (1B2PZ), 10% by mass of solid content of MEK solution), 5 parts of an amine alkoxysilane compound 240 parts of spherical silica (average particle diameter of 0.77 mu m, "SO-C2" manufactured by Adomex Co., Ltd.) surface-treated with a surfactant ("KBM573" manufactured by Kakugo Corporation) and 13 parts of a solution of an aromatic hydrocarbon resin (Y3) And uniformly dispersed with a rotary mixer to prepare a resin varnish. A resin sheet was prepared in the same manner as in Example 1.

[Comparative Example 1]

In Example 1,

1) The amount of spherical silica (average particle diameter 0.77 mu m, "SO-C2" manufactured by Adomex Co., Ltd.) surface-treated with an amine alkoxysilane compound (KBM573 manufactured by Shin-Etsu Chemical Co., Ltd.) was changed from 220 parts to 240 parts Change,

2) The amount of naphthol-type epoxy resin ("ESN475V" manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., epoxy equivalent: about 330) was changed from 40 parts to 50 parts,

3) 10 parts of an aromatic hydrocarbon resin ("ESN375" manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., epoxy equivalent weight: about 171) was not used.

A resin varnish and a resin sheet were produced in the same manner as in Example 1 except for the above.

[Comparative Example 2]

In Example 2,

1) The amount of spherical silica (average particle diameter 0.77 mu m, "SO-C2" manufactured by Adomex Co., Ltd.) surface-treated with an amine alkoxysilane compound (KBM573 manufactured by Shin-Etsu Chemical Co., Ltd.) was changed from 220 parts to 240 parts Change,

2) The amount of naphthol-type epoxy resin ("ESN475V" manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., epoxy equivalent: about 330) was changed from 40 parts to 50 parts,

3) 10 parts of an aromatic hydrocarbon resin ("ESN375" manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., epoxy equivalent weight: about 171) was not used.

A resin varnish and a resin sheet were produced in the same manner as in Example 2 except for the above.

[Comparative Example 3]

In Example 3,

1) The amount of spherical silica (average particle diameter 0.77 mu m, "SO-C2" manufactured by Adomex Co., Ltd.) surface-treated with an amine alkoxysilane compound (KBM573 manufactured by Shin-Etsu Chemical Co., Ltd.) was changed from 220 parts to 240 parts Change,

2) The amount of naphthol-type epoxy resin ("ESN475V" manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., epoxy equivalent: about 330) was changed from 40 parts to 50 parts,

3) 10 parts of an aromatic hydrocarbon resin ("ESN375" manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd., epoxy equivalent weight: about 171) was not used.

A resin varnish and a resin sheet were produced in the same manner as in Example 3 except for the above.

<Evaluation of Smear Removability>

(1) Under-processing of the built-in board

A glass cloth base epoxy resin double-sided copper clad laminate (thickness of copper foil of 18 mu m, thickness of the substrate: 0.8 mm, "R1515A" manufactured by Panasonic Corporation) having a copper foil on its surface was prepared as the inner layer board. The copper foil on the surface of the inner layer substrate was etched with a copper etching amount of 1 mu m using a microetching agent (&quot; CZ8101 &quot; Thereafter, drying was carried out at 190 캜 for 30 minutes.

(2) Lamination and curing of resin sheet

The resin sheets obtained in the above-described Examples and Comparative Examples were laminated by using a batch type vacuum press laminator (CVP700, 2 stage build-up laminator manufactured by Nikko Corporation) to bond the resin composition layer to the inner layer substrate, Both sides of the substrate were laminated. The laminate was subjected to pressure reduction for 30 seconds to bring the air pressure to 13 hPa or lower, followed by compression at a temperature of 100 deg. C and a pressure of 0.74 MPa for 30 seconds.

Subsequently, the laminated resin sheet was subjected to heat pressing under atmospheric pressure at 100 DEG C and a pressure of 0.5 MPa for 60 seconds to be smoothed. This was put in an oven at 100 캜, heated for 30 minutes, transferred to an oven at 170 캜, and heated for 30 minutes to form an insulating layer.

(3) Formation of via holes

An insulation layer was processed under the conditions of a frequency 2,000 Hz, a pulse width of 6 microseconds, an output of 0.24 mJ and a number of shots of 3 using a CO ₂ laser processing machine (LK-2K212 / 2C) manufactured by VIA MECHANICS Co., A top diameter (diameter) of 25 mu m, and a diameter at the bottom of the insulating layer of 19 mu m. The PET film of the support was then peeled off.

(4) Harmonization processing

The inner layer substrate was immersed in Swelling Dip · Sekrygant P manufactured by Atotech Japan Co., Ltd., which is a swelling liquid, at 60 ° C for 5 minutes. Subsequently, the resultant was immersed in a Concentrate Compact P (KMnO ₄ : 60 g / L, manufactured by Atotech Japan Co., Ltd., aqueous solution of NaOH: 40 g / L) for 20 minutes at 80 캜. Finally, the solution was immersed in a Reduction Solution · Sucry Gant P manufactured by Atotech Japan Co., Ltd. for 5 minutes at 40 ° C.

(5) Residual evaluation of the via hole bottom

The vicinity of the bottom of the via hole was observed with a scanning electron microscope (SEM), and the maximum smear diameter from the wall surface of the via hole bottom was measured from the obtained image and evaluated according to the following criteria.

?: Maximum smear length is less than 5 占 퐉

×: maximum smear length of 5 μm or more

&Lt; Measurement of dielectric loss tangent &

The resin sheet obtained in each of the Examples and Comparative Examples was thermally cured at 200 캜 for 90 minutes, and the PET film was peeled off to obtain a sheet-like cured product. The cured product was cut into test pieces having a width of 2 mm and a length of 80 mm. The CP521 and the network analyzer E8362B manufactured by Kanto Yodenshi Kaihatsu Co., Ltd. and the nitrogen analyzer manufactured by Agilent Technologies Co., Ltd. , Dielectric tangent (tan delta) was measured at a measurement frequency of 5.8 GHz by a cavity resonance method. Two test pieces were measured, and the average value was calculated.

The content (mass%) of the component (A) represents the content of the component (A) when the total content of the component (A) and the component (C) is 100 mass% (% By mass) "represents the content of the component (D) when the nonvolatile component in the resin composition is 100% by mass.

Even if the components (C) to (G) are not contained in Examples 1 to 6, it is confirmed that the results are the same as those of the above-mentioned Examples although there are differences in the degree.

Claims (18)

(A) an aromatic ring hydrocarbon resin containing an aromatic ring as a single ring or condensed ring and having two or more groups containing oxygen atoms bonded to the aromatic ring per one aromatic ring, and
(B) an active ester-based curing agent. The resin composition according to claim 1, wherein the component (A) has a structure represented by the following formula (1).
[Chemical Formula 1]

In Formula 1,
R ¹¹ each independently represents a monovalent group. The resin composition according to claim 1, wherein the component (A) has a structure represented by the following formula (2).
(2)

In Formula 2,
R ²¹ each independently represents a monovalent group. The resin composition according to claim 1, wherein the component (A) is represented by the following formula (3).
(3)

In Formula 3,
R ³¹ each independently represents a monovalent group,
R ³² each independently represents a divalent hydrocarbon group,
n3 is an integer of 0 to 10; The resin composition according to claim 1, wherein the component (A) is represented by the following formula (6).
[Chemical Formula 6]

In Formula 6,
R ⁶¹ each independently represents a monovalent group,
n6 is an integer of 0 to 10; The resin composition according to claim 1, wherein the group containing an oxygen atom bonded to the aromatic ring is an epoxyalkyleneoxy group, an alkoxy group, or a hydroxyl group. The resin composition according to claim 1, further comprising (C) an epoxy resin. The resin composition according to claim 7, wherein the content of the component (A) is 5% by mass or more and 50% by mass or less when the total content of the component (A) and the component (C) is 100% by mass. The resin composition according to claim 1, wherein the content of the component (B) is 1% by mass or more and 30% by mass or less when the content of the nonvolatile component in the resin composition is 100% by mass. The resin composition according to claim 1, further comprising (D) an inorganic filler. The resin composition according to claim 10, wherein the content of the component (D) is 50% by mass or more when the content of the nonvolatile component in the resin composition is 100% by mass. The resin composition according to claim 1, which is a resin composition for forming an insulating layer of a multilayered printed circuit board. The resin composition according to claim 1, which is a resin composition for forming an insulating layer having a via hole having a top diameter of 35 탆 or less. The resin composition according to claim 1, which is a resin composition for forming an insulating layer, having a via hole having a thickness (탆) of an insulating layer and an aspect ratio (thickness of an insulating layer / top diameter) of a top diameter (탆) of 0.5 or more. A resin sheet comprising a support and a resin composition layer comprising the resin composition according to any one of claims 1 to 14 provided on the support. The resin sheet according to claim 15, wherein the thickness of the resin composition layer is 20 占 퐉 or less. A printed wiring board comprising an insulating layer formed by a cured product of the resin composition according to any one of claims 1 to 14. A semiconductor device comprising the printed wiring board according to claim 17.