KR20220134455A - Resin composition - Google Patents

Abstract

Provided is a resin composition (for forming an interlayer insulating layer of a printed wiring board), capable of obtaining a cured product having a low dielectric loss tangent and excellent smear removability and elongation at break. The resin composition is for forming an interlayer insulating layer of a printed wiring board, and includes (A) an epoxy resin, (B) an active ester compound, and (C) an inorganic filler, wherein the component (A) contains (A-1) an epoxy resin represented by chemical formula (1). In the chemical formula (1), the definition of each symbol is as described in the specification.

Description

Resin composition {RESIN COMPOSITION}

The present invention relates to a resin composition containing an epoxy resin. Moreover, it is related with the resin sheet obtained using the said resin composition, a printed wiring board, and a semiconductor device.

As a manufacturing technique of a printed wiring board, the manufacturing method by the buildup system which piles up an insulating layer and a conductor layer alternately is known. In the manufacturing method by a build-up method, generally, an insulating layer is formed by hardening|curing a resin composition. In recent years, suppressing the dielectric loss tangent of an insulating layer to a lower level is calculated|required.

[Patent Document 1] Japanese Patent Laid-Open No. 2018-197282 [Patent Document 2] International Publication No. 2020/129724

Until now, it is known that the dielectric loss tangent of the insulating layer can be suppressed lower by using an epoxy resin composition containing an active ester compound as a resin composition for forming the insulating layer (Patent Document 1). However, when the epoxy resin composition which mix|blended the active ester compound was used, the fall of smear removability, the fall of elongation at break, etc. became a subject.

On the other hand, 2,6-xylenol dicyclopentadiene type epoxy resin is known until now (patent document 2).

An object of the present invention is to provide a resin composition (for forming an interlayer insulating layer of a printed wiring board) from which a dielectric loss tangent is suppressed low and a cured product having excellent smear removability and elongation at break can be obtained.

In order to achieve the subject of this invention, as a result of earnest examination, the present inventors contain (A) an epoxy resin, (B) an active ester compound, and (C) an inorganic filler, and (A) component is described below By using a resin composition containing a specific epoxy resin, it was unexpectedly found that a cured product having a low dielectric loss tangent and excellent smear removability and elongation at break can be obtained, and the present invention has been completed.

That is, the present invention includes the following contents.

[1] A resin composition comprising (A) an epoxy resin, (B) an active ester compound, and (C) an inorganic filler,

(A) component, (A-1) formula (1):

[In formula (1),

R ¹ each independently represents a hydrogen atom, a group represented by the formula (1a), or a group represented by the formula (1b), and at least one R ¹ is a group represented by the formula (1a), or the formula is the group represented by (1b):

(In formulas (1a) and (1b), * represents a binding site.);

R ² and R ³ each independently represent a hydrocarbon group having 1 to 8 carbon atoms;

n is an integer of 0 or more and represents the number of repeating units.]

A resin composition for forming an interlayer insulating layer of a printed wiring board, comprising an epoxy resin represented by .

[2] The resin composition for forming an interlayer insulating layer of a printed wiring board according to the above [1], wherein the average value of n is in the range of 0 to 5.

[3] The resin composition for forming an interlayer insulating layer of a printed wiring board according to the above [1] or [2], wherein the component (A) further contains a liquid epoxy resin at a temperature below 20°C.

[4] The printed wiring board according to any one of [1] to [3], wherein the content of the component (A) is 1% by mass to 30% by mass when the nonvolatile component in the resin composition is 100% by mass. A resin composition for forming an interlayer insulating layer.

[5] Formation of an interlayer insulating layer of the printed wiring board according to any one of [1] to [4], wherein the content of component (B) is 5% by mass or more when the nonvolatile component in the resin composition is 100% by mass. for resin composition.

[6] The resin composition for forming an interlayer insulating layer of a printed wiring board according to any one of [1] to [5], wherein the component (C) is silica.

[7] Formation of an interlayer insulating layer of the printed wiring board according to any one of [1] to [6], wherein the content of component (C) is 40% by mass or more when the nonvolatile component in the resin composition is 100% by mass. for resin composition.

[8] The resin composition for forming an interlayer insulating layer of a printed wiring board according to any one of [1] to [7], further comprising a phenoxy resin.

[9] The resin composition for forming an interlayer insulating layer of a printed wiring board according to any one of [1] to [8], further comprising a phenol-based curing agent.

[10] For forming an interlayer insulating layer of the printed wiring board according to any one of [1] to [9], wherein the elongation at break of the cured product of the resin composition is 1.0% or more when measured at 23° C. in accordance with JIS K7127. resin composition.

[11] The resin for forming an interlayer insulating layer of the printed wiring board according to any one of [1] to [10], wherein the dielectric loss tangent (Df) of the cured product of the resin composition is 0.0040 or less when measured at 5.8 GHz and 23°C composition.

[12] The resin for forming an interlayer insulating layer of the printed wiring board according to any one of [1] to [11], wherein the dielectric constant (Dk) of the cured product of the resin composition is 3.5 or less when measured at 5.8 GHz and 23°C composition.

[13] A resin sheet having a support and a resin composition layer provided on the support, comprising:

The resin composition layer contains (A) an epoxy resin, (B) an active ester compound, and (C) an inorganic filler,

(A) component, (A-1) formula (1):

[In formula (1),

R ¹ each independently represents a hydrogen atom, a group represented by the formula (1a), or a group represented by the formula (1b), and at least one R ¹ is a group represented by the formula (1a), or the formula is the group represented by (1b):

(In formulas (1a) and (1b), * represents a binding site.);

R ² and R ³ each independently represent a hydrocarbon group having 1 to 8 carbon atoms;

n is an integer of 0 or more and represents the number of repeating units.]

A resin sheet for forming an interlayer insulating layer of a printed wiring board, which is a resin composition layer formed of a resin composition containing an epoxy resin represented by .

[14] A resin composition comprising (A) an epoxy resin, (B) an active ester compound, and (C) an inorganic filler,

(A) component, (A-1) formula (1):

[In formula (1),

R ¹ each independently represents a hydrogen atom, a group represented by the formula (1a), or a group represented by the formula (1b), and at least one R ¹ is a group represented by the formula (1a), or the formula is the group represented by (1b):

(In formulas (1a) and (1b), * represents a binding site.);

R ² and R ³ each independently represent a hydrocarbon group having 1 to 8 carbon atoms;

n is an integer of 0 or more and represents the number of repeating units.]

A printed wiring board comprising an insulating layer made of a cured product of a resin composition containing an epoxy resin represented by .

[15] A semiconductor device comprising the printed wiring board according to the above [14].

ADVANTAGE OF THE INVENTION According to the resin composition of this invention, dielectric loss tangent is suppressed low, and the hardened|cured material which has the outstanding smear removability and the elongation at break can be obtained.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail based on the suitable embodiment. However, this invention is not limited to the following embodiment and an illustration, The range which does not deviate from the range which does not deviate from the claim of this invention and its equivalent range can be implemented by changing arbitrarily.

<Resin composition>

The resin composition of the present invention is a resin composition for forming an interlayer insulating layer of a printed wiring board (resin composition for forming an interlayer insulating layer of a printed wiring board). On the other hand, in the present invention, the interlayer insulating layer of the printed wiring board also includes the rewiring forming layer of the semiconductor package.

The resin composition of the present invention contains (A) an epoxy resin, (B) an active ester compound, and (C) an inorganic filler, and the component (A) contains a specific epoxy resin (A-1) described below do. By using such a resin composition, a cured product having a low dielectric loss tangent and excellent smear removability and elongation at break can be obtained.

The resin composition of this invention may contain further arbitrary components other than (A) an epoxy resin, (B) an active ester compound, and (C) an inorganic filler. As arbitrary components, (B') other hardening|curing agent, (D) thermoplastic resin, (E) hardening accelerator, (F) other additive, and (G) organic solvent are mentioned, for example. Hereinafter, each component contained in a resin composition is demonstrated in detail.

<(A) Epoxy resin>

The resin composition of this invention contains (A) an epoxy resin. (A) Epoxy resin is an epoxy equivalent of 5,000 g/eq. It is curable resin which has the following epoxy groups.

<(A-1) Specific Epoxy Resin>

In the resin composition of the present invention, (A) the epoxy resin is (A-1) general formula (1):

[In formula (1),

R ¹ each independently represents a hydrogen atom, a group represented by the formula (1a), or a group represented by the formula (1b), and at least one R ¹ is a group represented by the formula (1a), or the formula is the group represented by (1b):

(In formulas (1a) and (1b), * represents a binding site.);

R ² and R ³ each independently represent a hydrocarbon group having 1 to 8 carbon atoms;

n is an integer of 0 or more and represents the number of repeating units.]

contains an epoxy resin represented by (hereinafter sometimes referred to as "specific epoxy resin"). The unit represented by n may be the same or different for every unit.

R ¹ each independently represents a hydrogen atom, a group represented by the formula (1a), or a group represented by the formula (1b), and at least one R ¹ is a group represented by the formula (1a), or the formula It is a group represented by (1b).

R ² and R ³ each independently represent a hydrocarbon group having 1 to 8 carbon atoms. R ² and R ³ are each independently, preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group, more preferably a methyl group, an ethyl group, a propyl group, or an isopropyl group, still more preferably a methyl group to be.

The hydrocarbon group is a monovalent group having only carbon atoms as skeletal atoms, and may include a straight-chain structure, a branched-chain structure and/or a cyclic structure, and may be a group not containing an aromatic ring or a group containing an aromatic ring. Examples of the hydrocarbon group having 1 to 8 carbon atoms include an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an aralkyl group having 7 or 8 carbon atoms, an alkylaryl group having 7 or 8 carbon atoms, and a phenyl group.

The alkyl group means a linear, branched and/or cyclic monovalent aliphatic saturated hydrocarbon group. A C1-C6 alkyl group is preferable, and, as for a C1-C8 alkyl group, a C1-C3 alkyl group is more preferable. Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, and a jade group. tyl group, cyclopentyl group, cyclohexyl group, 4-methylcyclohexyl group, 2,4-dimethylcyclohexyl group, cyclopentylmethyl group, cyclohexylmethyl group, etc. are mentioned.

The alkenyl group means a straight-chain, branched-chain and/or cyclic monovalent aliphatic unsaturated hydrocarbon group having at least one carbon-carbon double bond. A C2-C6 alkenyl group is preferable and, as for a C2-C8 alkenyl group, a C2-C8 alkenyl group is more preferable. Examples of the alkenyl group having 2 to 8 carbon atoms include a vinyl group, a propenyl group (allyl group, 1-propenyl group, isopropenyl group), butenyl group (1-butenyl group, crotyl group, methallyl group, isocrotyl group, etc.) ), pentenyl group (such as 1-pentenyl group), hexenyl group (such as 1-hexenyl group), heptenyl group (such as 1-heptenyl group), octenyl group (such as 1-octenyl group), cyclopentenyl group (2- cyclopentenyl group etc.), cyclohexenyl group (3-cyclohexenyl group etc.), etc. are mentioned.

The aralkyl group means a monovalent aliphatic saturated hydrocarbon group substituted with a monovalent aromatic hydrocarbon group composed of an aromatic carbocyclic ring. Examples of the aralkyl group having 7 or 8 carbon atoms include a benzyl group, a phenethyl group, and an α-methylbenzyl group.

The alkylaryl group means a monovalent aromatic hydrocarbon group composed of an aromatic carbocyclic ring substituted with a monovalent aliphatic saturated hydrocarbon group. Examples of the alkylaryl group having 7 or 8 carbon atoms include 4-methylphenyl group, 3-methylphenyl group, 2-methylphenyl group, 2,4-dimethylphenyl group, 3,4-dimethylphenyl group, 4-ethylphenyl group, 3- An ethylphenyl group, 2-ethylphenyl group, etc. are mentioned.

n is an integer of 0 or more, and represents the number of repeating units. The average value of n is preferably 0 or more, more preferably 0.01 or more, still more preferably 0.1 or more, still more preferably 0.3 or more, still more preferably 0.5 or more, particularly preferably 0.6 or more, The upper limit is preferably 5 or less, more preferably 2 or less, still more preferably 1.5 or less, particularly preferably 1 or less.

(A-1) The epoxy equivalent of a specific epoxy resin becomes like this. Preferably it is 3,700 g/eq. or less, More preferably, it is 2,000 g/eq. or less, Especially preferably, it is 700 g/eq. or less, and a minimum is specifically limited. Although not necessarily, it is preferably 244 g/eq. above, more preferably 260 g/eq. or more, particularly preferably 270 g/eq. or more. Epoxy equivalent is the mass of resin per equivalent of epoxy group. This epoxy equivalent can be measured according to JISK7236.

(A-1) A specific epoxy resin can be manufactured using the method described in International Publication No. 2020/129724, or a method equivalent thereto, for example.

Although content of (A-1) specific epoxy resin with respect to all non-volatile components in a resin composition is not specifically limited, When the non-volatile component in a resin composition is 100 mass %, Preferably it is 50 mass % or less, More Preferably it is 40 mass % or less, More preferably, it is 30 mass % or less, More preferably, it is 20 mass % or less, Especially preferably, it is 15 mass % or less. Although the lower limit of content of (A-1) specific epoxy resin with respect to all non-volatile components is not specifically limited, When the non-volatile component in a resin composition is 100 mass %, from a viewpoint of acquiring the effect of this invention more remarkably , Preferably it is 0.1 mass % or more, More preferably, it is 0.5 mass % or more, More preferably, it is 1 mass % or more, More preferably, it is 3 mass % or more, Especially preferably, it is 5 mass % or more.

Although content of (A-1) specific epoxy resin with respect to all (A) epoxy resin in a resin composition is not specifically limited, When all (A) epoxy resin in a resin composition is 100 mass %, Preferably 90 It is mass % or less, More preferably, it is 80 mass % or less, Especially preferably, it is 70 mass % or less. Although the lower limit of content of (A-1) specific epoxy resin with respect to all (A) epoxy resin is not specifically limited, When all (A) epoxy resin in a resin composition is 100 mass %, the effect of this invention is From a viewpoint of obtaining more significantly, Preferably it is 10 mass % or more, More preferably, it is 30 mass % or more, Especially preferably, it is 50 mass % or more.

<(A-2) Other Epoxy Resins>

The resin composition of this invention WHEREIN: (A) Epoxy resin may contain (A-2) other epoxy resin as arbitrary components. (A-2) Other epoxy resins are components which do not correspond to (A-1) component.

(A-2) Examples of other epoxy resins include bixylenol-type epoxy resins, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, bisphenol S-type epoxy resins, bisphenol AF-type epoxy resins, and dicyclopentadiene epoxy resins. , Trisphenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type Epoxy resin, glycidyl ester type epoxy resin, cresol novolak type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, butadiene structure epoxy resin, alicyclic epoxy resin, heterocyclic epoxy Resin, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, isocyanurate type epoxy resin, phenol A phthalimidine type epoxy resin etc. are mentioned. (A-2) Other epoxy resins may be used individually by 1 type, and may be used in combination of 2 or more type.

It is preferable that the resin composition contains the epoxy resin which has two or more epoxy groups in 1 molecule as another epoxy resin (A-2). (A-2) The ratio of the epoxy resin having two or more epoxy groups in one molecule with respect to 100% by mass of the other nonvolatile components of the epoxy resin is preferably 50% by mass or more, more preferably 60% by mass or more, Especially preferably, it is 70 mass % or more.

Epoxy resins include a liquid epoxy resin (hereinafter sometimes referred to as “liquid epoxy resin”) at a temperature of 20°C or lower, and a solid epoxy resin at a temperature of 20°C or lower (hereinafter referred to as “solid epoxy resin”). .) is there. (A) The epoxy resin is (A-2) other epoxy resins, and may contain only a liquid epoxy resin, or may contain only a solid epoxy resin, or a combination of a liquid epoxy resin and a solid epoxy resin it's okay to do (A) It is preferable that an epoxy resin contains a liquid epoxy resin as (A-2) another epoxy resin.

As a liquid epoxy resin, the liquid epoxy resin which has two or more epoxy groups in 1 molecule is preferable.

Examples of the liquid epoxy resin include glycyrole-type epoxy resin, bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol AF-type epoxy resin, naphthalene-type epoxy resin, glycidyl ester-type epoxy resin, glycidylamine-type epoxy resin, Preferred are phenol novolak-type epoxy resins, alicyclic epoxy resins having an ester skeleton, cyclohexanedimethanol-type epoxy resins, cyclic aliphatic glycidyl ethers, and epoxy resins having a butadiene structure, glycyrole-type epoxy resins, and cyclic aliphatic Glycidyl ether, a bisphenol A epoxy resin, and a bisphenol F epoxy resin are more preferable.

As a specific example of a liquid epoxy resin, "EX-992L" by Nagase Chemtex, "YX7400" by Mitsubishi Chemical, "HP4032" by DIC, "HP4032D", "HP4032SS" (naphthalene type epoxy resin); "828US", "828EL", "jER828EL", "825", "Epicoat 828EL" (bisphenol A epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER807", "1750" (bisphenol F type) manufactured by Mitsubishi Chemical epoxy resin); "jER152" by Mitsubishi Chemical (phenol novolak type epoxy resin); "630", "630LSD", and "604" (glycidylamine type epoxy resin) by Mitsubishi Chemical Corporation; "ED-523T" by ADEKA (glycyrol type epoxy resin); "EP-3950L" by ADEKA, "EP-3980S" (glycidylamine type epoxy resin); "EP-4088S" by ADEKA (dicyclopentadiene type epoxy resin); "ZX1059" (mixture of a bisphenol A epoxy resin and a bisphenol F type epoxy resin) by the Nitetsu Chemical & Materials company; "EX-721" by the Nagase Chemtex company (glycidyl ester type epoxy resin); "EX-991L" manufactured by Nagase Chemtex Co., Ltd. (epoxy resin containing alkyleneoxy skeleton and butadiene skeleton); "Celoxide 2021P" by Daicel (alicyclic epoxy resin which has ester skeleton); "PB-3600" by Daicel Corporation, "JP-100" by Nippon Soda Corporation, "JP-200" (epoxy resin having a butadiene structure); "ZX1658", "ZX1658GS" (liquid 1, 4- glycidyl cyclohexane type epoxy resin) by the Nitetsu Chemical & Materials company; "EG-280" by Osaka Gas Chemicals (fluorene structure containing epoxy resin); "EX-201" (cyclic aliphatic glycidyl ether) by the Nagase Chemtex company etc. are mentioned.

As a solid epoxy resin, the solid epoxy resin which has 3 or more epoxy groups in 1 molecule is preferable, and the aromatic solid epoxy resin which has 3 or more epoxy groups in 1 molecule is more preferable.

Examples of the solid epoxy resin include a bixylenol type epoxy resin, a naphthalene type epoxy resin, a naphthalene type tetrafunctional epoxy resin, a naphthol novolak type epoxy resin, a cresol novolak type epoxy resin, a dicyclopentadiene type epoxy resin, a trisphenol type epoxy resin , Naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, phenol aralkyl type epoxy resin, tetraphenylethane type epoxy resin, phenol A phthalimidine type epoxy resin is preferable.

As a specific example of a solid epoxy resin, "HP4032H" by DIC (naphthalene type epoxy resin); "HP-4700", "HP-4710" by DIC company (naphthalene type tetrafunctional epoxy resin); "N-690" by DIC (cresol novolak-type epoxy resin); "N-695" by DIC (cresol novolak-type epoxy resin); "HP-7200", "HP-7200HH", "HP-7200H", "HP-7200L" (dicyclopentadiene type epoxy resin) manufactured by DIC Corporation; "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" by DIC company (naphthylene ether type epoxy resin); "EPPN-502H" by a Nippon Kayaku company (trisphenol type epoxy resin); "NC7000L" by a Nippon Kayaku company (naphthol novolak-type epoxy resin); "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin) by a Nippon Kayaku company; "ESN475V", "ESN4100V" (naphthalene type epoxy resin) by the Nitetsu Chemical & Materials company; "ESN485" (naphthol type epoxy resin) by the Nitetsu Chemical & Materials company; "ESN375" (dihydroxynaphthalene epoxy resin) by the Nitetsu Chemical & Materials company; "YX4000H", "YX4000", "YX4000HK", "YL7890" by Mitsubishi Chemical Corporation (bixylenol type epoxy resin); "YL6121" by Mitsubishi Chemical (biphenyl type epoxy resin); "YX8800" by Mitsubishi Chemical (anthracene type epoxy resin); "YX7700" by Mitsubishi Chemical (phenol aralkyl type epoxy resin); "PG-100" and "CG-500" manufactured by Osaka Gas Chemicals; "YL7760" (bisphenol AF type|mold epoxy resin) by a Mitsubishi Chemical company; "YL7800" by Mitsubishi Chemical (fluorene type epoxy resin); "jER1010" manufactured by Mitsubishi Chemical Corporation (bisphenol A epoxy resin); "jER1031S" by Mitsubishi Chemical (tetraphenylethane type epoxy resin); "WHR991S" (phenol phthalimidine type epoxy resin) by a Nippon Kayaku company, etc. are mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more type.

(A-2) As other epoxy resins, when a liquid epoxy resin and a solid epoxy resin are used in combination, their mass ratio (liquid epoxy resin: solid epoxy resin) is preferably 10:1 to 1:50, more preferably preferably from 2:1 to 1:20, particularly preferably from 1:1 to 1:10.

(A-2) The epoxy equivalent of another epoxy resin becomes like this. Preferably it is 50 g/eq. - 5,000 g/eq., More preferably, it is 60 g/eq. to 2,000 g/eq., more preferably 70 g/eq. to 1,000 g/eq., even more preferably 80 g/eq. to 500 g/eq. Epoxy equivalent is the mass of resin per equivalent of epoxy group. This epoxy equivalent can be measured according to JISK7236.

(A-2) The weight average molecular weight (Mw) of another epoxy resin becomes like this. Preferably it is 100-5,000, More preferably, it is 250-3,000, More preferably, it is 400-1,500. The weight average molecular weight of resin can be measured as a polystyrene conversion value by the gel permeation chromatography (GPC) method.

Although content of (A-2) other epoxy resin with respect to all non-volatile components in a resin composition is not specifically limited, When the non-volatile component in a resin composition is 100 mass %, Preferably it is 30 mass % or less, More Preferably it is 10 mass % or less, Especially preferably, it is 5 mass % or less. Although the lower limit of content of (A-2) other epoxy resin with respect to all non-volatile components is not specifically limited, When the non-volatile component in a resin composition is 100 mass %, for example, 0 mass % or more, 0.01 It is mass % or more, Preferably it is 0.1 mass % or more, More preferably, it is 1 mass % or more, Especially preferably, it is 3 mass % or more.

Although content of (A) epoxy resin with respect to all the non-volatile components in a resin composition is not specifically limited, When the non-volatile component in a resin composition is 100 mass %, Preferably it is 70 mass % or less, More preferably It is 50 mass % or less, More preferably, it is 30 mass % or less, More preferably, it is 20 mass % or less, Especially preferably, it is 15 mass % or less. Although the lower limit of content of (A) epoxy resin with respect to all non-volatile components is not specifically limited, When the non-volatile component in a resin composition is 100 mass %, Preferably it is 0.1 mass % or more, More preferably, 0.5 It is mass % or more, More preferably, it is 1 mass % or more, More preferably, it is 5 mass % or more, Especially preferably, it is 10 mass % or more.

<(B) active ester compound>

The resin composition of the present invention contains (B) an active ester compound. (B) An active ester compound may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios. (B) The active ester compound may have a function as an epoxy resin curing agent that is cured by reacting with the (A) epoxy resin.

(B) As an active ester compound, in general, two or more ester groups with high reaction activity, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of a heterocyclic hydroxy compound, in 1 molecule A compound having a compound is preferably used. It is preferable that the said active ester compound is obtained by the condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound, and a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester compound obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester compound obtained from a carboxylic acid compound, 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, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene type diphenol compound, phenol novolac, etc. are mentioned. Here, a "dicyclopentadiene type diphenol compound" means a diphenol compound obtained by condensing two molecules of phenol to one molecule of dicyclopentadiene.

Specifically, (B) as the active ester compound, a dicyclopentadiene-type active ester compound, a naphthalene-type active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and benzoyl of phenol novolac An active ester compound containing a compound is preferable, and among these, at least one selected from a dicyclopentadiene-type active ester compound and a naphthalene-type active ester compound is more preferable, and a dicyclopentadiene-type active ester compound is still more preferable. do. As the dicyclopentadiene-type active ester compound, an active ester compound containing a dicyclopentadiene-type diphenol structure is preferable.

(B) Commercially available active ester compounds are active ester compounds containing a dicyclopentadiene-type diphenol structure, such as "EXB9451", "EXB9460", "EXB9460S", "EXB-8000L", "EXB-8000L-65M" ”, “EXB-8000L-65TM”, “HPC-8000L-65TM”, “HPC-8000”, “HPC-8000-65T”, “HPC-8000H”, “HPC-8000H-65TM”, (manufactured by DIC) ); As an active ester compound containing a naphthalene structure, "HP-B-8151-62T", "EXB-8100L-65T", "EXB-8150-60T", "EXB-8150-62T", "EXB-9416-70BK" , "HPC-8150-60T", "HPC-8150-62T", "EXB-8" (manufactured by DIC Corporation); "EXB9401" (manufactured by DIC Corporation) as a phosphorus-containing active ester compound, "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound that is an acetylated product of phenol novolac, "YLH1026" , "YLH1030", "YLH1048" (manufactured by Mitsubishi Chemical), "PC1300-02-65MA" (manufactured by Air Water Corporation), etc. as an active ester compound containing a styryl group and a naphthalene structure.

(B) The active ester group equivalent of the active ester compound is preferably 50 g/eq. to 500 g/eq., more preferably 50 g/eq. to 400 g/eq., more preferably 100 g/eq. to 300 g/eq. The active ester group equivalent is the mass of the active ester compound per equivalent of the active ester group.

The content of the (B) active ester compound relative to all nonvolatile components in the resin composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, when the nonvolatile component in the resin composition is 100% by mass, More preferably, it is 5 mass % or more, Especially preferably, it is 8 mass % or more. Although the upper limit of content of (B) active ester compound with respect to all non-volatile components is not specifically limited, When the non-volatile component in a resin composition is 100 mass %, Preferably it is 50 mass % or less, More preferably It is 40 mass % or less, More preferably, it is 30 mass % or less, More preferably, it is 25 mass % or less, Especially preferably, it is 20 mass % or less.

The mass ratio of the (B) active ester compound to the (A) epoxy resin in the resin composition (component (B)/component (A)) is preferably 0.05 or more, more preferably 0.1 or more, particularly preferably 0.5 or more. to be. The upper limit of the mass ratio (component (B)/component (A)) of the (B) active ester compound to the (A) epoxy resin in the resin composition is preferably 5 or less, more preferably 3 or less, particularly preferably 1 or less.

<(B') other curing agent>

The resin composition of this invention may contain the (B') hardening|curing agent other than (B) component further as an arbitrary component. (B') Other hardening|curing agents may be used individually by 1 type, and may be used in combination of 2 or more types arbitrarily. (B') Other hardening agents may have a function as an epoxy resin hardening|curing agent which reacts with (A) an epoxy resin and hardens similarly to (B) an active ester compound.

(B') The other curing agent is not particularly limited, but for example, a phenol-based curing agent, a carbodiimide-based curing agent, an acid anhydride-based curing agent, an amine-based curing agent, a benzoxazine-based curing agent, a cyanate ester-based curing agent, and a thiol and curing agents. It is especially preferable that the resin composition of this invention contains a phenol type hardening|curing agent from a viewpoint of improving more sclerosis|hardenability of a resin composition.

As a phenolic hardening|curing agent, the phenolic hardening|curing agent which has a novolak structure from a viewpoint of heat resistance and water resistance is preferable. Moreover, from a viewpoint of the adhesiveness to a to-be-adhered body, a nitrogen-containing phenolic hardening|curing agent is preferable, and a triazine skeleton containing phenolic hardening|curing agent is more preferable. Among them, a triazine skeleton-containing phenol novolac resin is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesiveness. As a specific example of a phenolic hardening|curing agent, For example, "MEH-7700", "MEH-7810", "MEH-7851" by Meiwa Kasei Corporation, "NHN" by Nippon Kayaku Corporation, "CBN", "GPH" ', "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-375" manufactured by Nittetsu Chemical & Materials. ', "SN-395", "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P", "LA-1356", "TD2090", "TD2090" manufactured by DIC Corporation -2090-60M" etc. are mentioned.

Examples of the carbodiimide-based curing agent include curing agents having one or more, preferably two or more carbodiimide structures in one molecule, for example, tetramethylene-bis(t-butylcarbodiimide); aliphatic biscarbodiimides such as cyclohexanebis(methylene-t-butylcarbodiimide); biscarbodiimides such as aromatic biscarbodiimides such as phenylene-bis(xylylcarbodiimide); Aliphatic polycarbodiimides such as polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylenecarbodiimide, poly(methylenebiscyclohexylenecarbodiimide), and poly(isophoronecarbodiimide) ; Poly(phenylenecarbodiimide), poly(naphthylenecarbodiimide), poly(tolylenecarbodiimide), poly(methyldiisopropylphenylenecarbodiimide), poly(triethylphenylenecarbodiimide) , poly(diethylphenylenecarbodiimide), poly(triisopropylphenylenecarbodiimide), poly(diisopropylphenylenecarbodiimide), poly(xylylenecarbodiimide), poly(tetramethyl) polycarbodiimides such as aromatic polycarbodiimides such as xylylenecarbodiimide), poly(methylenediphenylenecarbodiimide), and poly[methylenebis(methylphenylene)carbodiimide].

As a commercial item of a carbodiimide type hardening|curing agent, "Carbodilite V-02B", "Carbodilite V-03", "Carbodilite V-04K", "Carbodilite" by Nisshinbo Chemical Co., Ltd. product, for example, are, for example, V-07" and "Carbodilite V-09"; "Stabakusol P", "Stabakusol P400", "Hicardil 510" by the Rhein-Chemistry company, etc. are mentioned.

Examples of the acid anhydride curing agent include curing agents having one or more acid anhydride groups in one molecule, and curing agents having two or more acid anhydride groups in one molecule are preferable. Specific examples of the acid anhydride curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, and trialkyltetrahydrophthalic anhydride. , dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, trimellitic anhydride, pyromellitic anhydride , benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,3,3a ,4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl)-naphtho [1,2-C] furan-1,3-dione, ethylene glycol bis ( anhydrotrimellitate), and polymer-type acid anhydrides, such as styrene maleic acid resin which copolymerized styrene and maleic acid, etc. are mentioned. As a commercial item of an acid anhydride type hardening|curing agent, "HNA-100", "MH-700", "MTA-15", "DDSA", "OSA" by Shin-Nippon Rika Corporation, "YH-306" by Mitsubishi Chemical Corporation , "YH-307", "HN-2200", "HN-5500" manufactured by Hitachi Kasei, "EF-30", "EF-40", "EF-60", "EF-80" manufactured by Clay Valei and the like.

Examples of the amine-based curing agent include curing agents having one or more, preferably two or more amino groups in one molecule, for example, aliphatic amines, polyetheramines, alicyclic amines, aromatic amines, and the like. Among them, aromatic amines are preferable from the viewpoint of exhibiting the desired effect of the present invention. Primary amine or secondary amine is preferable and, as for an amine type hardening|curing agent, primary amine is more preferable. Specific examples of the amine curing agent include 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'- Diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobi Phenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3 -Dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane , 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis( 4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, etc. are mentioned. A commercial item may be used for an amine hardening|curing agent, For example, "SEIKACURE-S" by Seika Corporation, "KAYABOND C-200S" by Nippon Kayaku Corporation, "KAYABOND C-100", "Kayahard A-A", "Kaya Hard A-B", "Kaya Hard A-S", "Epicure W" by Mitsubishi Chemical, etc. are mentioned.

As a specific example of a benzoxazine type hardening|curing agent, "JBZ-OP100D" by JFE Chemicals, "ODA-BOZ"; "HFB2006M" by Showa Kobunshi Corporation; "P-d", "F-a" manufactured by Shikoku Kaseiko Co., Ltd., etc. are mentioned.

Examples of the cyanate ester curing agent include bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4,4'-methylenebis(2,6). -Dimethylphenylcyanate), 4,4'-ethylidenediphenyldicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4 -Cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4- Bifunctional cyanate resins such as cyanatephenyl)thioether and bis(4-cyanatephenyl)ether, polyfunctional cyanate resins derived from phenol novolac and cresol novolac, etc., these cyanate resins are partially triazined One prepolymer, etc. are mentioned. Specific examples of the cyanate ester curing agent include "PT30" and "PT60" (both phenol novolac-type polyfunctional cyanate ester resins) manufactured by Ronza Japan, "BA230", "BA230S75" (bisphenol A dicyanate prepolymer))) etc. in which a part or all of it was triazineized and became a trimer.

Examples of the thiol-based curing agent include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), tris(3-mercaptopropyl)isocyanurate, and the like. can

(B') The reactive weight of the other curing agent is preferably 50 g/eq. to 3000 g/eq., more preferably 100 g/eq. to 1000 g/eq., more preferably 100 g/eq. to 500 g/eq., particularly preferably 100 g/eq. to 300 g/eq. The reactor equivalent is the mass of the curing agent per equivalent of the reactor.

Although content of (B') other hardening|curing agent with respect to all non-volatile components in the resin composition is not specifically limited, When the non-volatile component in a resin composition is 100 mass %, Preferably it is 20 mass % or less, More preferably is 10 mass % or less, more preferably 5 mass % or less, particularly preferably 3 mass % or less The lower limit of the content of (B') other curing agent with respect to the total non-volatile component is not particularly limited, but the resin When the non-volatile component in the composition is 100 mass %, for example, it may be 0 mass % or more, 0.01 mass % or more, 0.1 mass % or more, 1 mass % or more.

The content of the (B) active ester compound relative to the total curing agent in the resin composition is preferably 100% by mass of the total curing agent in the resin composition (that is, the total of (B) active ester compound and (B') other curing agent). is 10 mass % or more, More preferably, it is 30 mass % or more, More preferably, it is 40 mass % or more, Especially preferably, it is 50 mass % or more.

<(C) Inorganic filler>

The resin composition of this invention contains (C) an inorganic filler. (C) The inorganic filler is contained in the resin composition in the state of particle|grains.

(C) As a material of an inorganic filler, an inorganic compound is used. (C) As the material of the inorganic filler, for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, hydroxide Aluminum, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, Barium titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium phosphate tungstate, etc. are mentioned. Among these, silica is particularly suitable. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Moreover, as a silica, spherical silica is preferable. (C) An inorganic filler may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios.

(C) As a commercial item of an inorganic filler, For example, "UFP-30" by a Denka Chemical Industry Co., Ltd.; "SP60-05", "SP507-05" by the Shin-Nitetsu Sumikin Materials company; "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by Adomatex Corporation; "UFP-30" by Denka Corporation; "Silly writing NSS-3N", "Silly writing NSS-4N", "Silly writing NSS-5N" manufactured by Tokuyama Corporation; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1" manufactured by Adomatex Corporation; "DAW-03" by Denka Corporation, "FB-105FD", etc. are mentioned.

(C) The average particle diameter of the inorganic filler is not particularly limited, but is preferably 10 µm or less, more preferably 5 µm or less, still more preferably 2 µm or less, still more preferably 1 µm or less, particularly Preferably it is 0.7 micrometer or less. (C) The lower limit of the average particle diameter of the inorganic filler is not particularly limited, but is preferably 0.01 µm or more, more preferably 0.05 µm or more, still more preferably 0.1 µm or more, particularly preferably 0.2 µm or more. . (C) The average particle diameter of an inorganic filler can be measured by the laser diffraction/scattering method based on the Mie scattering theory. Specifically, it can measure by creating the particle diameter distribution of an inorganic filler on a volume basis with a laser diffraction scattering type particle diameter distribution measuring apparatus, and making the median diameter into an average particle diameter. As the measurement sample, 100 mg of inorganic filler and 10 g of methyl ethyl ketone were put in a vial bottle, and what was dispersed for 10 minutes by ultrasonic wave can be used. Measure the sample to be measured using a laser diffraction particle size distribution measuring device, using a light source wavelength of blue and red, measuring the volume-based particle size distribution of the inorganic filler by a flow cell method, and measuring the median diameter from the obtained particle size distribution The average particle diameter was calculated as As a laser diffraction type particle size distribution measuring apparatus, "LA-960" by Horiba Corporation, etc. are mentioned, for example.

(C) The specific surface area of the inorganic filler is not particularly limited, but preferably 0.1 m 2 /g or more, more preferably 0.5 m 2 /g or more, still more preferably 1 m 2 /g or more, particularly preferably 3 m2/g or more. (C) The upper limit of the specific surface area of the inorganic filler is not particularly limited, but is preferably 100 m 2 /g or less, more preferably 70 m 2 /g or less, still more preferably 50 m 2 /g or less, particularly preferably is 40 m 2 /g or less. The specific surface area of the inorganic filler can be obtained by adsorbing nitrogen gas to the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountec) in accordance with the BET method, and calculating the specific surface area using the BET multi-point method. have.

(C) It is preferable that the inorganic filler is treated with the surface treating agent from a viewpoint of improving moisture resistance and dispersibility. As the surface treatment agent, for example, a fluorine-containing silane coupling agent, an aminosilane-based coupling agent, an epoxysilane-based coupling agent, a mercaptosilane-based coupling agent, a silane-based coupling agent, an alkoxysilane, an organosilazane compound, a titanate-based coupler A ring agent etc. are mentioned. In addition, a surface treatment agent may be used individually by 1 type, and may be used combining two or more types arbitrarily.

As a commercial item of a surface treatment agent, For example, Shin-Etsu Chemical Co., Ltd. "KBM403" (3-glycidoxypropyl trimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM803" (3-mercaptopropyltrimethoxy) silane), "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical “SZ-31” (hexamethyldisilazane) manufactured by Kogyo Co., Ltd. “KBM103” (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. “KBM-4803” manufactured by Shin-Etsu Chemical Co., Ltd. (long-chain epoxy type silane couple) Ring agent), "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., N-phenyl-8-aminooctyltrimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd., etc. can be heard

It is preferable that the grade of the surface treatment by a surface treatment agent falls within a predetermined range from a viewpoint of the dispersibility improvement of an inorganic filler. Specifically, 100% by mass of the inorganic filler is preferably surface-treated with a surface treatment agent of 0.2% by mass to 5% by mass, more preferably surface-treated at 0.2% by mass to 3% by mass, 0.3% by mass It is more preferable that it is surface-treated at -2 mass %.

The grade of the surface treatment by a surface treating agent can be evaluated by the amount of carbon per unit surface area of an inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m 2 or more, more preferably 0.1 mg/m 2 or more, and still more preferably 0.2 mg/m 2 or more. On the other hand, from the viewpoint of preventing an increase in melt viscosity of the resin composition or melt viscosity in sheet form, 1.0 mg/m 2 or less is preferable, 0.8 mg/m 2 or less is more preferable, and 0.5 mg/m 2 or less is still more preferable. .

(C) The amount of carbon per unit surface area of an inorganic filler can be measured, after washing-processing the inorganic filler after surface treatment with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, MEK in a sufficient amount as a solvent is added to the inorganic filler surface-treated with a surface treatment agent, followed by ultrasonic cleaning at 25°C for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As a carbon analyzer, "EMIA-320V" by Horiba Corporation, etc. can be used.

Although content of (C) inorganic filler with respect to all the non-volatile components in a resin composition is not specifically limited, When the non-volatile component in a resin composition is 100 mass %, Preferably it is 90 mass % or less, More preferably 85% by mass or less, more preferably 80% by mass or less, particularly preferably 75% by mass or less. Although the lower limit of content of (C) inorganic filler with respect to all non-volatile components is not specifically limited, When the non-volatile component in a resin composition is 100 mass %, Preferably it is 40 mass % or more, More preferably, 50 It is mass % or more, More preferably, it is 60 mass % or more, More preferably, it is 65 mass % or more, Especially preferably, it is 70 mass % or more.

The mass ratio (component (C)/component (A)) of the (C) inorganic filler to the (A) epoxy resin in the resin composition is preferably 0.5 or more, more preferably 1 or more, particularly preferably 3 or more. . The upper limit of the mass ratio (component (C)/component (A)) of the (C) inorganic filler to the (A) epoxy resin in the resin composition is preferably 50 or less, more preferably 30 or less, particularly preferably 10 or less. is below.

<(D) Thermoplastic resin>

The resin composition of the present invention may further contain (D) the thermoplastic resin as an optional component. (D) thermoplastic resin demonstrated here is a component which does not correspond to (A) epoxy resin.

(D) As the thermoplastic resin, for example, polyimide resin, phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, Polyphenylene ether resin, polycarbonate resin, polyether ether ketone resin, polyester resin, etc. are mentioned. In one Embodiment, it is preferable that the resin composition of this invention contains the thermoplastic resin chosen from the group which consists of a polyimide resin and a phenoxy resin, It is more preferable that a phenoxy resin is included. In addition, a thermoplastic resin may be used individually by 1 type, or may be used in combination of 2 or more type.

Specific examples of the polyimide resin include "SLK-6100" by Shin-Etsu Chemical Co., Ltd., "Ricacoat SN20" and "Licacoat PN20" by Rika Shin-Nippon.

Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolak skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene. and phenoxy resins having at least one skeleton selected from the group consisting of skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, and trimethylcyclohexane skeleton. Any functional group, such as a phenolic hydroxyl group and an epoxy group, may be sufficient as the terminal of a phenoxy resin.

Specific examples of the phenoxy resin include "1256" and "4250" manufactured by Mitsubishi Chemical (both are bisphenol A skeleton-containing phenoxy resins); "YX8100" by a Mitsubishi Chemical company (bisphenol S skeleton containing phenoxy resin); "YX6954" by a Mitsubishi Chemical company (bisphenolacetophenone skeleton containing phenoxy resin); "FX280" and "FX293" manufactured by Shin-Nittetsu Sumikin Chemical Co., Ltd.; "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7482" and "YL7891BH30" manufactured by Mitsubishi Chemical Corporation; and the like.

As polyvinyl acetal resin, polyvinyl formal resin and polyvinyl butyral resin are mentioned, for example, Polyvinyl butyral resin is preferable. Specific examples of the polyvinyl acetal resin include "Denka Butyral 4000-2", "Denka Butyral 5000-A", "Denka Butyral 6000-C", "Denka Butyral 6000-EP" manufactured by Denki Chemical Co., Ltd. ; S-Rec BH series, BX series (eg BX-5Z), KS series (eg KS-1), BL series, BM series manufactured by Sekisui Chemical Co., Ltd.; and the like.

Examples of the polyolefin resin include ethylene-based copolymer resins such as low-density polyethylene, ultra-low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-methyl acrylate copolymer; Polyolefin polymers, such as a polypropylene and an ethylene-propylene block copolymer, etc. are mentioned.

Examples of the polybutadiene resin include a hydrogenated polybutadiene skeleton-containing resin, a hydroxyl group-containing polybutadiene resin, a phenolic hydroxyl group-containing polybutadiene resin, a carboxyl group-containing polybutadiene resin, an acid anhydride group-containing polybutadiene resin, and an epoxy group-containing polybutadiene. Resin, isocyanate group containing polybutadiene resin, urethane group containing polybutadiene resin, polyphenylene ether- polybutadiene resin, etc. are mentioned.

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

As a specific example of polyether sulfone resin, the Sumitomo Chemical Company "PES5003P" etc. are mentioned.

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

As a specific example of polyphenylene ether resin, SABIC "NORYL SA90" etc. are mentioned. Specific examples of the polyetherimide resin include "Urtem" manufactured by GE Corporation.

Examples of the polycarbonate resin include a hydroxyl group-containing carbonate resin, a phenolic hydroxyl group-containing carbonate resin, a carboxyl group-containing carbonate resin, an acid anhydride group-containing carbonate resin, an isocyanate group-containing carbonate resin, and a urethane group-containing carbonate resin. Specific examples of the polycarbonate resin include "FPC0220" manufactured by Mitsubishi Gas Chemical, "T6002", "T6001" (polycarbonate diol) manufactured by Asahi Kasei, "C-1090", "C-2090" manufactured by Kuraray Corporation. , "C-3090" (polycarbonate diol), etc. are mentioned. As a specific example of polyether ether ketone resin, "Sumiproy K" by Sumitomo Chemical Co., Ltd., etc. are mentioned.

Examples of the polyester resin include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polytrimethylene terephthalate resin, polytrimethylene naphthalate resin, polycyclohexanedimethyl tere. A phthalate resin etc. are mentioned.

(D) the weight average molecular weight (Mw) of the thermoplastic resin is preferably 5,000 or more, more preferably 8,000 or more, still more preferably 10,000 or more, particularly preferably 20,000 or more, from the viewpoint of significantly obtaining the effect of the present invention, , preferably 100,000 or less, more preferably 70,000 or less, still more preferably 60,000 or less, particularly preferably 50,000 or less.

Although content of (D) thermoplastic resin with respect to all the non-volatile components in a resin composition is not specifically limited, When the non-volatile component in a resin composition is 100 mass %, Preferably it is 20 mass % or less, More preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, particularly preferably 3% by mass or less. Although the lower limit of content of (D) thermoplastic resin with respect to all non-volatile components is not specifically limited, When the non-volatile component in a resin composition is 100 mass %, For example, 0 mass % or more, 0.01 mass % or more , 0.1 mass % or more, 1 mass % or more, and the like.

<(E) curing accelerator>

The resin composition of this invention may contain the (E) hardening accelerator as an arbitrary component. (E) A hardening accelerator has a function as a hardening catalyst which accelerates|stimulates hardening of (A) an epoxy resin.

(E) As a hardening accelerator, a phosphorus type hardening accelerator, a urea type hardening accelerator, a guanidine type hardening accelerator, an imidazole type hardening accelerator, a metal type hardening accelerator, an amine type hardening accelerator, etc. are mentioned, for example. (E) The curing accelerator preferably contains a curing accelerator selected from imidazole-based curing accelerators and amine-based curing accelerators, and particularly preferably contains an amine-based curing accelerator. (E) A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the phosphorus-based curing accelerator include tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphoniumdecanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium)pyro melitate, tetrabutylphosphonium hydrogen hexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, di-tert-butylmethylphosphonium aliphatic phosphonium salts such as tetraphenylborate; Methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra- p-tolyl borate, tetraphenylphosphonium tetraphenyl borate, tetraphenylphosphonium tetrap-tolyl borate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphoniumtetraphenylborate, tris(2-methyl aromatic phosphonium salts such as oxyphenyl)ethylphosphoniumtetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate; aromatic phosphine/borane complexes such as triphenylphosphine/triphenylborane; Aromatic phosphine-quinone addition reactants, such as a triphenylphosphine/v-benzoquinone addition reactant; tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl (2-butenyl) phosphine, di-tert-butyl (3-methyl-2-butenyl) phosphine, aliphatic phosphines such as tricyclohexylphosphine; Dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolyl Phosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-isopropylphenyl)phosphine, Tris(4-butylphenyl)phosphine, tris(4-tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,5-dimethylphenyl)phosphine, tris(2, 6-dimethylphenyl)phosphine, tris(3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine , tris (2-methoxyphenyl) phosphine, tris (4-methoxyphenyl) phosphine, tris (4-ethoxyphenyl) phosphine, tris (4-tert-butoxyphenyl) phosphine, diphenyl- 2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2- Aromatic phosphines, such as bis (diphenyl phosphino) acetylene and 2,2'- bis (diphenyl phosphino) diphenyl ether, etc. are mentioned.

Examples of the urea-based curing accelerator include 1,1-dimethylurea; aliphatic dimethylureas such as 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, and 3-cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3- Chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, 3-(3,4 -Dimethylphenyl)-1,1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4 -Nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]- 1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N',N'-dimethylurea ), an aromatic dimethylurea such as N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluenebisdimethylurea], and the like.

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, and diphenylguanidine. , 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, 1-(o-tolyl)biguanide, etc. are mentioned.

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methyl. Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Imidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2- Ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimida Zolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-unde Silimidazolyl-(1′)]-ethyl-s-triazine, 2,4-diamino-6-[2′-ethyl-4′-methylimidazolyl-(1′)]-ethyl-s -triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazineisocyanuric acid adduct, 2-phenylimidazoleisocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1, 2-a] imidazole compounds such as benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline and 2-phenylimidazoline, imidazole compounds and epoxy resins and an adduct body with

As the imidazole-based curing accelerator, a commercially available product may be used, for example, “1B2PZ”, “2MZA-PW”, “2PHZ-PW” manufactured by Shikoku Kasei Co., Ltd., “P200-H50” manufactured by Mitsubishi Chemical Company, etc. can be heard

As a metal type hardening accelerator, the organometallic complex or organometallic salt of metals, such as cobalt, copper, zinc, iron, nickel, manganese, and tin, is mentioned, for example. Specific examples of the organometallic complex include organocobalt complexes such as cobalt(II)acetylacetonate and cobalt(III)acetylacetonate, organocopper complexes such as copper(II)acetylacetonate, and zinc(II)acetylacetonate. Organic iron complexes, such as an organic zinc complex, iron(III) acetylacetonate, organic nickel complexes, such as nickel (II) acetylacetonate, organic manganese complexes, such as manganese (II) acetylacetonate, etc. are mentioned. Examples of the organometallic salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

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

A commercial item may be used as an amine type hardening accelerator, For example, "MY-25" by Ajinomoto Fine Techno, etc. is mentioned.

Although content of (E) hardening accelerator in a resin composition is not specifically limited, When the nonvolatile component in a resin composition is 100 mass %, Preferably it is 5 mass % or less, More preferably, it is 1 mass % or less, More Preferably it is 0.5 mass % or less, Especially preferably, it is 0.1 mass % or less. Although the lower limit of content of (E) hardening accelerator in a resin composition is not specifically limited, When the non-volatile component in a resin composition is 100 mass %, For example, 0 mass % or more, 0.001 mass % or more, 0.01 mass % or more.

<(F) Other additives>

The resin composition of this invention may contain arbitrary additives further as a non-volatile component. Examples of such additives include thermosetting resins such as epoxy acrylate resins, urethane acrylate resins, urethane resins, cyanate resins, benzoxazine resins, unsaturated polyester resins, phenol resins, melamine resins, silicone resins, and epoxy resins. ; a radically polymerizable compound having 4-vinylphenyl, an acryloyl group, a methacryloyl group, a maleimide group (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl group) or the like; radical polymerization initiators such as peroxide radical polymerization initiators and azo radical polymerization initiators; organic fillers such as rubber particles; organometallic compounds such as an organocopper compound, an organozinc compound, and an organocobalt compound; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as silicone-based leveling agents and acrylic polymer-based leveling agents; thickeners such as bentone and montmorillonite; Antifoaming agents, such as a silicone type antifoamer, an acrylic type antifoamer, a fluorine type antifoamer, and a vinyl resin type antifoamer; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; adhesion improvers such as urea silane; adhesion-imparting agents such as triazole-based adhesion-imparting agents, tetrazole-based adhesion-imparting agents, and triazine-based adhesion-imparting agents; antioxidants such as hindered phenolic antioxidants; optical brighteners such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; Flame retardants such as phosphorus-based flame retardants (eg, phosphoric acid ester compounds, phosphazene compounds, phosphinic acid compounds, red), nitrogen-based flame retardants (eg, melamine sulfate), halogen-based flame retardants, and inorganic flame retardants (eg, antimony trioxide) ; dispersants such as phosphoric acid ester dispersants, polyoxyalkylene dispersants, acetylene dispersants, silicone dispersants, anionic dispersants, and cationic dispersants; and stabilizers such as borate stabilizers, titanate stabilizers, aluminate stabilizers, zirconate stabilizers, isocyanate stabilizers, carboxylic acid stabilizers, and carboxylic acid anhydride stabilizers. (F) Other additives may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios. (F) If it is a person skilled in the art, content of other additives can be set suitably.

<(G) organic solvent>

The resin composition of this invention may contain further arbitrary organic solvents as a volatile component other than the nonvolatile component mentioned above. (G) As an organic solvent, a well-known thing can be used suitably, The kind is not specifically limited. (G) Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, and anisole; alcohol solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; ether ester solvents such as 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, and methyl methoxypropionate; ester alcohol solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, and diethylene glycol monobutyl ether (butyl carbitol); amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane and methylcyclohexane; and aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene and trimethylbenzene. (G) The organic solvent may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios.

Although content of (G) organic solvent in the varnish-like resin composition before drying is not specifically limited, When all the components in a resin composition are 100 mass %, For example, 40 mass % or less, 30 mass % or less, Preferably Preferably it is 20 mass % or less, More preferably, it is 10 mass % or less, More preferably, it is 8 mass % or less, Especially preferably, it is 6 mass % or less. Although content of (G) organic solvent in the resin composition which forms the resin composition layer after drying in a resin sheet is not specifically limited, When all the components in a resin composition are 100 mass %, Preferably 5 mass % or less, More preferably, it is 3 mass % or less, More preferably, it is 2 mass % or less, Especially preferably, it is 1 mass % or less.

<Method for producing a resin composition>

The resin composition of the present invention may be prepared, for example, in an arbitrary preparation container with (A) an epoxy resin, (B) an active ester compound, (C) an inorganic filler, optionally (D) a thermoplastic resin, and optionally (E) It can manufacture by adding and mixing a hardening accelerator, (F) other additive as needed, and (G) organic solvent as needed in arbitrary order and/or part or all simultaneously. In addition, in the process of adding and mixing each component, temperature can be set suitably, and you may heat and/or cool over temporarily or continuously. In addition, in the process of adding and mixing, or after that, the resin composition may be stirred or shaken using, for example, stirring apparatuses, such as a mixer, or a shaking apparatus, and may be disperse|distributed uniformly. Further, at the same time as stirring or shaking, defoaming may be performed under low pressure conditions such as under vacuum.

<Characteristics of the resin composition>

The resin composition of the present invention contains (A) an epoxy resin, (B) an active ester compound, and (C) an inorganic filler, and the component (A) contains the specific epoxy resin (A-1) described above . By using such a resin composition, a cured product having a low dielectric loss tangent and excellent smear removability and elongation at break can be obtained.

The cured product of the resin composition of the present invention may have a characteristic of being excellent in elongation at break. Therefore, in one embodiment, when the elongation at break of the cured product of the resin composition of the present invention is measured at 23° C. according to JIS K7127 as in Test Example 3 below, preferably 0.5% or more, more preferably 0.8% or more, more preferably 1.0% or more, even more preferably 1.2% or more, particularly preferably 1.4% or more. The upper limit of the elongation at break can be usually 10% or less, 5% or less, or the like.

The hardened|cured material of the resin composition of this invention may have the characteristic that it is excellent in smear removability. Therefore, in one embodiment, as in Test Example 2 below, a via hole having a top diameter of 50 μm on the surface of the cured product and a diameter of 40 μm on the bottom of the via hole is formed, and after roughening, the maximum from the wall surface of the bottom of the via hole When the smear length is measured, the maximum smear length may be less than 5 μm.

The cured product of the resin composition of the present invention may have a low dielectric loss tangent (Df). Therefore, in one embodiment, the dielectric loss tangent (Df) of the cured product of the resin composition when measured at 5.8 GHz and 23° C. as in Test Example 1 below is preferably 0.0100 or less, 0.0080 or less, more preferably 0.0070 or less. or less, 0.0060 or less, more preferably 0.0050 or less, 0.0045 or less, particularly preferably 0.0040 or less, and 0.0035 or less.

In one embodiment, the cured product of the resin composition of the present invention may have a characteristic that the dielectric constant (Dk) is low. Therefore, in one embodiment, the dielectric constant (Dk) of the cured product of the resin composition when measured at 5.8 GHz and 23° C. as in Test Example 1 below is preferably 5.0 or less, more preferably 4.5 or less, further Preferably it is 4.0 or less, More preferably, it is 3.7 or less, Especially preferably, it may be 3.5 or less and 3.4 or less.

<Resin sheet>

Although the resin composition of this invention can be apply|coated and used in the state of a varnish, it is suitable industrially generally to use it with the form of the resin sheet containing the said resin composition.

The resin sheet of the present invention is a resin sheet for forming an interlayer insulating layer of a printed wiring board (resin sheet for forming an interlayer insulating layer of a printed wiring board).

In one Embodiment, a resin sheet has a support body and the resin composition layer provided on the said support body, The resin composition layer is formed from the resin composition demonstrated above.

The thickness of the resin composition layer is preferably 50 µm or less, more preferably 40 µm or less, from the viewpoint of reducing the thickness of the printed wiring board and providing a cured product excellent in insulation even if the cured product of the resin composition is a thin film. . Although the lower limit of the thickness of a resin composition layer is not specifically limited, Usually, it can be 5 micrometers or more, 10 micrometers or more, etc.

As a support body, the film which consists of a plastic material, metal foil, and a release paper are mentioned, for example, The film which consists of a plastic material, and metal foil are preferable.

When a film made of a plastic material is used as the support, the plastic material is, for example, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyethylene naphthalate (hereinafter sometimes abbreviated as “PEN”). .) polyester, polycarbonate (hereinafter, may be abbreviated as “PC”), acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES) ), polyether ketone, polyimide, and the like. Among these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

When using metal foil as a support body, as metal foil, copper foil, aluminum foil, etc. are mentioned, for example, Copper foil is preferable. As the copper foil, a foil made of a single metal of copper may be used, or a foil made of an alloy of copper and another metal (eg, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. good night.

A support body may give a mat treatment, a corona treatment, and an antistatic treatment to the surface to join with the resin composition layer.

Moreover, as a support body, you may use the support body with a mold release layer which has a mold release layer on the surface to join with a resin composition layer. As a mold release agent used for the mold release layer of a support body with a mold release layer, 1 or more types of mold release agents are mentioned from the group which consists of an alkyd resin, a polyolefin resin, a urethane resin, and a silicone resin, for example. The support with a release layer may use a commercial item, for example, "SK-1", "AL-5", "AL-" manufactured by Lintec which is a PET film which has a release layer which has an alkyd resin type mold release agent as a main component. 7", "Lumira T60" by Tore Corporation, "Purex" by Teijin Corporation, "Unipil" by Unichika Corporation, etc. are mentioned.

Although the thickness of a support body is not specifically limited, The range of 5 micrometers - 75 micrometers is preferable, and the range of 10 micrometers - 60 micrometers is more preferable. On the other hand, when using a support body with a mold release layer, it is preferable that the thickness of the whole support body with a mold release layer is the said range.

In one embodiment, the resin sheet may further contain arbitrary layers as needed. As such an arbitrary layer, the protective film according to the support body etc. which were provided in the surface which is not joined to the support body of a resin composition layer (that is, the surface on the opposite side to a support body), etc. are mentioned, for example. Although the thickness of a protective film is not specifically limited, For example, they are 1 micrometer - 40 micrometers. By laminating|stacking a protective film, adhesion of dust, etc. to the surface of a resin composition layer, and a flaw can be suppressed.

A resin sheet is, for example, a liquid resin composition as it is, or a resin varnish obtained by dissolving a resin composition in an organic solvent is prepared, this is applied on a support using a die coater or the like, and further dried to form a resin composition layer It can be manufactured by forming.

As an organic solvent, the thing similar to the organic solvent demonstrated as a component of a resin composition is mentioned. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

You may perform drying by well-known methods, such as a heating and hot air spraying. Although drying conditions are not specifically limited, Content of the organic solvent in a resin composition layer is 10 mass % or less, Preferably, it is dried so that it may become 5 mass % or less. Although it changes also depending on the boiling point of the organic solvent in a resin composition or resin varnish, for example, when using the resin composition or resin varnish containing 30 mass % - 60 mass % of an organic solvent, 50 degreeC - 150 degreeC for 3 minutes to 10 minutes By drying, a resin composition layer can be formed.

A resin sheet can be wound up and stored in roll shape. When a resin sheet has a protective film, it becomes usable by peeling off a protective film.

<Printed wiring board>

The printed wiring board of this invention contains the insulating layer which consists of hardened|cured material obtained by hardening|curing the resin composition of this invention.

A printed wiring board can be manufactured by the method including the process of following (I) and (II) using the above-mentioned resin sheet, for example.

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

(II) Step of curing (eg, thermosetting) the resin composition layer to form an insulating layer

The "inner-layer substrate" used in step (I) is a member used as a substrate for a printed wiring board, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene. An ether substrate etc. are mentioned. Moreover, the said board|substrate may have a conductor layer on the one side or both surfaces, and this conductor layer may be pattern-processed. An inner-layer substrate in which a conductor layer (circuit) is formed on one or both surfaces of the substrate is sometimes referred to as an "inner-layer circuit board". In addition, when manufacturing a printed wiring board, the intermediate manufactured product in which an insulating layer and/or a conductor layer should further be formed is also included in the "inner-layer board|substrate" referred to in this invention. When a printed wiring board is a component-embedded circuit board, you may use the inner-layer board which incorporated components.

Lamination of the inner layer substrate and the resin sheet can be performed, for example, by heat-compressing the resin sheet to the inner layer substrate from the support side. As a member (hereinafter also referred to as a "thermocompression bonding member") which heat-compresses a resin sheet to an inner-layer board|substrate, a heated metal plate (SUS mirror plate etc.), a metal roll (SUS roll), etc. are mentioned, for example. On the other hand, it is preferable not to press the thermocompression-bonding member directly to the resin sheet, but to press through an elastic material, such as a heat-resistant rubber, so that the resin sheet may fully follow the surface unevenness|corrugation of an inner-layer board|substrate.

You may perform lamination|stacking of an inner-layer board|substrate and a resin sheet by the vacuum lamination method. In the vacuum lamination method, the thermocompression compression temperature is preferably in the range of 60°C to 160°C, more preferably 80°C to 140°C, and the thermocompression compression pressure is preferably 0.098 MPa to 1.77 MPa, more preferably is in the range of 0.29 MPa to 1.47 MPa, and the heat compression time is preferably in the range of 20 seconds to 400 seconds, and more preferably in the range of 30 seconds to 300 seconds. The lamination may be preferably carried out under reduced pressure conditions of a pressure of 26.7 hPa or less.

Lamination can be performed with a commercially available vacuum laminator. As a commercially available vacuum laminator, the vacuum pressure laminator by the Meiki Sesakusho company, the vacuum applicator by the Nikko Materials company, a batch type vacuum pressure laminator, etc. are mentioned, for example.

After lamination, a smoothing treatment of the laminated resin sheet may be performed under normal pressure (under atmospheric pressure), for example, by pressing the thermocompression-bonding member from the support side. The press conditions of the smoothing process can be made into the conditions similar to the thermocompression-bonding conditions of the said lamination|stacking. A smoothing process can be performed with a commercially available laminator. In addition, the lamination|stacking and smoothing process may be performed continuously using the above-mentioned commercially available vacuum laminator.

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

Step (II) WHEREIN: The resin composition layer is hardened (for example, thermosetting), and the insulating layer which consists of a hardened|cured material of a resin composition is formed. Curing conditions of a resin composition layer are not specifically limited, You may use the conditions normally employ|adopted by forming the insulating layer of a printed wiring board.

For example, although the thermosetting conditions of the resin composition layer also vary depending on the type of resin composition, etc., in one embodiment, the curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, More preferably, it is 170 degreeC - 210 degreeC. The curing time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, still more preferably 15 minutes to 100 minutes.

Before thermosetting a resin composition layer, you may preheat a resin composition layer at temperature lower than hardening temperature. For example, prior to thermosetting the resin composition layer, at a temperature of 50 ° C. to 120 ° C., preferably 60 ° C. to 115 ° C., more preferably 70 ° C. to 110 ° C., for 5 minutes or more, Preferably, you may preheat for 5 minutes - 150 minutes, More preferably, it is 15 minutes - 120 minutes, More preferably, you may preheat for 15 minutes - 100 minutes.

When manufacturing a printed wiring board, you may perform further the process of (III) the process of drilling into an insulating layer, (IV) the process of roughening an insulating layer, and (V) the process of forming a conductor layer. You may implement these process (III) - process (V) according to various methods well-known to those skilled in the art used for manufacture of a printed wiring board. On the other hand, when the support is removed after the step (II), the removal of the support is carried out between the steps (II) and (III), between the steps (III) and (IV), or between the steps (IV) and the step (V). ) may be performed between In addition, if necessary, the formation of the insulating layer and the conductor layer in the steps (II) to (V) may be repeated to form a multilayer wiring board.

In another embodiment, the printed wiring board of this invention can be manufactured using the above-mentioned prepreg. The manufacturing method is basically the same as that in the case of using a resin sheet.

Step (III) is a step of drilling holes in the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. Step (III) may be performed using, for example, a drill, laser, plasma, etc. depending on the composition of the resin composition used for forming the insulating layer. You may determine the dimension and shape of a hole suitably according to the design of a printed wiring board.

Process (IV) is a process of roughening an insulating layer. Usually, in this process (IV), the removal of smear is also performed. The procedure and conditions of a roughening process are not specifically limited, When forming the insulating layer of a printed wiring board, the well-known procedure and conditions normally used are employable. For example, the swelling process by a swelling liquid, the roughening process by an oxidizing agent, and the neutralization process by a neutralizing liquid can be performed in this order, and an insulating layer can be roughened.

Although it does not specifically limit as a swelling liquid used for a roughening process, An alkali solution, surfactant solution, etc. are mentioned, Preferably it is an alkali solution, As said alkali solution, sodium hydroxide solution and potassium hydroxide solution are more preferable. As a commercially available swelling liquid, "Swelling Deep Security P", "Swelling Deep Security SBU" by Atotech Japan, etc. are mentioned, for example. Although the swelling process by a swelling liquid is not specifically limited, For example, it can perform by immersing an insulating layer in a 30 degreeC-90 degreeC swelling liquid for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling solution at 40°C to 80°C for 5 minutes to 15 minutes.

Although it does not specifically limit as an oxidizing agent used for a roughening process, For example, the alkaline permanganate solution which melt|dissolved potassium permanganate or sodium permanganate in the aqueous solution of sodium hydroxide is mentioned. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60°C to 100°C for 10 minutes to 30 minutes. Moreover, as for the density|concentration of the permanganate in an alkaline permanganic acid solution, 5 mass % - 10 mass % are preferable. As a commercially available oxidizing agent, alkaline permanganic acid solutions, such as "concentrate compact CP" and "dosing solution securigans P" by Atotech Japan, are mentioned, for example.

Moreover, as a neutralization liquid used for a roughening process, an acidic aqueous solution is preferable, and as a commercial item, "reduction solution securigant P" by Atotech Japan company is mentioned, for example.

The treatment with the neutralizing solution can be performed by immersing the treated surface subjected to the roughening treatment with the oxidizing agent in a neutralizing solution at 30°C to 80°C for 5 minutes to 30 minutes. The method of immersing the target object to which the roughening process by an oxidizing agent was carried out in the neutralization liquid of 40 degreeC - 70 degreeC from points, such as workability|operativity, for 5 minutes - 20 minutes is preferable.

In one embodiment, although the arithmetic mean roughness Ra of the insulating layer surface after a roughening process is not specifically limited, Preferably it is 500 nm or less, More preferably, it is 400 nm or less, More preferably, it is 300 nm or less. It does not specifically limit about a lower limit, For example, it can be set as 1 nm or more, 2 nm or more, etc. Moreover, the root mean square roughness (Rq) of the insulating layer surface after a roughening process becomes like this. Preferably it is 500 nm or less, More preferably, it is 400 nm or less, More preferably, it is 300 nm or less. It does not specifically limit about a lower limit, For example, it can be set as 1 nm or more, 2 nm or more, etc. The arithmetic mean roughness (Ra) and the root mean square roughness (Rq) of the surface of the insulating layer can be measured using a non-contact type surface roughness meter.

A process (V) is a process of forming a conductor layer, and forms a conductor layer on an insulating layer. The conductor material used for a conductor layer is not specifically limited. In a suitable embodiment, the conductor layer comprises one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. do. The conductor layer may be a single metal layer or an alloy layer, and the alloy layer is, for example, an alloy of two or more metals selected from the group described above (eg, nickel-chromium alloy, copper-nickel alloy, and copper-titanium). a layer formed of an alloy). Among them, from the viewpoints of versatility of conductor layer formation, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy, a copper-nickel alloy , a copper/titanium alloy alloy layer is preferable, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of a nickel/chromium alloy is more preferable, and a single metal layer of copper This is more preferable.

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

Although the thickness of a conductor layer depends on the design of a desired printed wiring board, it is 3 micrometers - 35 micrometers generally, Preferably it is 5 micrometers - 30 micrometers.

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 the insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method, and from the viewpoint of simplicity of manufacture, a semi-additive method It is preferable to form by the additive method. Hereinafter, an example in which a conductor layer is formed by a semi-additive method is shown.

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Then, on the formed plating seed layer, a mask pattern for exposing a part of the plating seed layer corresponding to the desired wiring pattern is formed. After forming a metal layer by electrolytic plating on the exposed plating seed layer, the mask pattern is removed. Thereafter, the unnecessary plating seed layer is removed by etching or the like to form a conductor layer having a desired wiring pattern.

In another embodiment, you may form a conductor layer using metal foil. When forming a conductor layer using metal foil, it is suitable to perform a process (V) between a process (I) and a process (II). For example, after a process (I), a support body is removed and metal foil is laminated|stacked on the surface of the exposed resin composition layer. You may perform lamination|stacking of a resin composition layer and metal foil by the vacuum lamination method. The lamination conditions may be the same as those described for the step (I). Then, step (II) is performed to form an insulating layer. Then, the conductor layer which has a desired wiring pattern can be formed by conventionally well-known techniques, such as a subtractive method and a modified semiadditive method, using the metal foil on an insulating layer.

Metal foil can be manufactured by well-known methods, such as an electrolytic method and a rolling method, for example. As a commercial item of metal foil, HLP foil, JXUT-III foil by a JX Nikko Nisseki Kinzoku company, 3EC-III foil by a Mitsui Kinzoku Kozan company, TP-III foil, etc. are mentioned, for example.

<Semiconductor device>

The semiconductor device of this invention contains the printed wiring board of this invention. The semiconductor device of this invention can be manufactured using the printed wiring board of this invention.

Examples of the semiconductor device include various semiconductor devices provided for electrical appliances (eg, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (eg, motorcycles, automobiles, trams, ships, and aircraft). have.

[Example]

Hereinafter, the present invention will be specifically described by way of Examples. The present invention is not limited to these examples. In addition, in the following, "part" and "%" which show quantity means "mass part" and "mass %", respectively, unless otherwise indicated. In the following description, the temperature condition is above normal temperature (25° C.) when there is no specific designation of temperature, and the pressure condition is below normal pressure (1 atm) when there is no specific designation of pressure.

<Synthesis Example 1: Synthesis of Epoxy Resin A>

95 parts of 2,6-xylenol and 6.3 parts of a 47% BF ₃ ether complex were poured into a reaction apparatus consisting of a glass separable flask equipped with a stirrer, a thermometer, a nitrogen blowing tube, a dropping funnel, and a cooling tube, while stirring Warm to 70°C. While maintaining the same temperature, 58.8 parts of dicyclopentadiene (0.56 times mole relative to 2,6-xylenol) was added dropwise over 1 hour. In addition, after reacting at a temperature of 115 to 125 ° C for 3 hours, 69.2 parts of dicyclopentadiene (0.67 times mole relative to 2,6-xylenol) was added dropwise in 1 hour at the same temperature, and the temperature of 115 ° C to 125 ° C. The reaction was carried out at the temperature for 2 hours. 1.0 part of calcium hydroxide was added, and also 2.0 part of 10% oxalic acid aqueous solution was added. Thereafter, it was heated to 160° C. for dehydration, and heated to 200° C. under a reduced pressure of 5 mmHg to evaporate and remove unreacted raw materials. To this, 520 parts of MIBK was added to dissolve the product, and 150 parts of 80°C hot water was added to wash with water, and the lower water layer was separated and removed. Then, under reduced pressure of 5 mmHg, it heated at 160 degreeC, MIBK was evaporated and removed, and 221 parts of reddish-brown phenol resin A was obtained. The hydroxyl equivalent was 377, the softening point was 102°C, and the absorption ratio (A ₃₀₄₀ /A ₁₂₁₀ ) was 0.18.

180 parts of phenol resin A, 221 parts of epichlorohydrin, and 33 parts of diethylene glycol dimethyl ether were added to the reaction apparatus provided with a stirrer, a thermometer, a nitrogen blowing tube, a dropping funnel, and a cooling tube, and it heated to 65 degreeC. 39 parts of 49% sodium hydroxide aqueous solution was dripped at the temperature of 63-67 degreeC under the reduced pressure of 125 mmHg over 4 hours. During this time, epichlorohydrin was azeotroped with water, and the effluent water was sequentially removed out of the system. After completion of the reaction, epichlorohydrin was recovered under the conditions of 5 mmHg and 180°C, and 482 parts of MIBK was added to dissolve the product. Thereafter, 146 parts of water was added to dissolve the salt by-product, and it was left still to separate and remove the salt solution of the lower layer. After neutralization with an aqueous phosphoric acid solution, the resin solution was washed with water until the washing solution became neutral, followed by filtration. It heated to 180 degreeC under reduced pressure of 5 mmHg, MIBK was distilled off, and 200 parts of red-brown transparent 2,6-xylenol dicyclopentadiene type epoxy resin (epoxy resin A) was obtained. Epoxy equivalent was 446 g/eq., total chlorine content 431 ppm, and it was resin with a softening point of 91 degreeC.

<Example 1: Preparation of resin composition 1>

20 parts of epoxy resin A synthesized in Synthesis Example 1 (epoxy equivalent: 446 g/eq.), 5 parts of bisphenol-based epoxy resin (“ZX-1059” manufactured by Nittetsu Chemical & Materials, about 165 g/eq. of epoxy equivalent), and 5 parts of biphenyl aralkyl-type epoxy resins ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 194 g/eq.) were dissolved by heating while stirring in 30 parts of solvent naphtha and 10 parts of cyclohexanone. Thereby, the epoxy resin solution was obtained.

After cooling to room temperature, in the epoxy resin solution, an inorganic filler (Spherical silica "SO-C2 manufactured by Adomatex Co., Ltd. surface-treated with N-phenyl-8-aminooctyltrimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd." ', specific surface area: 5.8 m / g, average particle diameter: 0.5 µm) 150 parts, an active ester curing agent (“HPC-8150-62T” manufactured by DIC Corporation, an active group equivalent of about 229 g/eq., a solid content of 62% by mass) 32 parts of toluene solution), 5 parts of a phenolic curing agent (“LA-3018-50P” manufactured by DIC, about 151 g/eq. , Mitsubishi Chemical Co., Ltd., 1:1 solution of MEK and cyclohexanone having a solid content of 30% by mass) 17 parts and a curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution having a solid content of 5% by mass) 0.6 parts are mixed, After uniformly disperse|distributing by the high-speed rotation mixer, it filtered with the cartridge filter ("SHP020" manufactured by ROKITECHNO), and the varnish-like resin composition 1 was prepared.

<Example 2: Preparation of resin composition 2>

In Example 1, in place of 32 parts of an active ester-based curing agent (“HPC-8150-62T” manufactured by DIC, an active group equivalent of about 229 g/eq., a toluene solution having a solid content of 62% by mass), an active ester-based curing agent (manufactured by DIC) 31 parts of "HPC-8000-65T", an active group equivalent of about 223 g/eq., and a toluene solution having a solid content of 65% by mass) were used. Except for the above, it carried out similarly to Example 1, and the varnish-form resin composition 2 was prepared.

<Comparative Example 1: Preparation of resin composition 3>

In Example 1, 20 parts of bisphenol AF type epoxy resin ("NC-3000", manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 275 g/eq.) was used instead of 20 parts of epoxy resin A (epoxy equivalent: 446 g/eq.) . A varnish-like resin composition 3 was prepared in the same manner as in Example 1 except for the above.

<Comparative Example 2: Preparation of resin composition 4>

In Example 1, instead of 20 parts of epoxy resin A (epoxy equivalent 446 g/eq.), 20 parts of naphthol aralkyl type epoxy resin ("ESN-475V" manufactured by Nittetsu Chemical & Materials, epoxy equivalent of about 330 g/eq.) was used. A varnish-like resin composition 4 was prepared in the same manner as in Example 1 except for the above.

<Comparative Example 3: Preparation of resin composition 5>

In Comparative Example 2, in place of 32 parts of an active ester-based curing agent (“HPC-8150-62T” manufactured by DIC, an active group equivalent of about 229 g/eq., a toluene solution having a solid content of 62% by mass), an active ester-based curing agent (manufactured by DIC) 31 parts of "HPC-8000-65T", an active group equivalent of about 223 g/eq., and a toluene solution having a solid content of 65% by mass) were used. Except for the above, it carried out similarly to the comparative example 2, and prepared the varnish-form resin composition 5.

<Production Example 1: Preparation of a resin sheet>

PET film (“Lumira R80” manufactured by Toray Corporation, 38 μm thick, softening point 130° C., hereinafter referred to as “Releasable PET”) treated with an alkyd resin mold release agent (“AL-5” manufactured by Lintec Co., Ltd.) as a support body .) was prepared.

The resin composition prepared in Examples and Comparative Examples was uniformly coated on the release PET with a die coater so that the thickness of the resin composition layer after drying was 25 μm, and dried at 80° C. for 1 minute, thereby forming the resin composition layer on the release PET. formed. Next, the rough surface of the polypropylene film ("Alpan MA-411" manufactured by Oji Ftex Corporation, 15 µm thick) as a protective film is bonded to the resin composition layer on the surface that is not bonded to the support of the resin composition layer. laminated. Thereby, the resin sheet which consists of mold release PET (support body), the resin composition layer, and the protective film in order was produced.

<Test Example 1: Measurement and evaluation of dielectric constant and dielectric loss tangent>

After peeling off a protective film from the resin sheet created in Production Example 1, heating at 200 degreeC for 90 minutes and thermosetting the resin composition layer, the support body was peeled. The obtained cured product was cut into a test piece having a width of 2 mm and a length of 80 mm. With respect to the said test piece, the dielectric constant (Dk) and dielectric loss tangent (Df) were measured at the measurement frequency of 5.8 GHz and the measurement temperature of 23 degreeC by the cavity resonance perturbation method using "HP8362B" manufactured by Agilent Technologies. The three test pieces were measured, the average value was computed, and the following evaluation criteria evaluated based on the said average value.

Evaluation standard

「○」: When the relative dielectric constant (Dk) is 3.5 or less and the dielectric loss tangent (Df) is 0.0040 or less

「×」: When the relative dielectric constant (Dk) exceeds 3.5 or the dielectric loss tangent (Df) exceeds 0.0040

<Test Example 2: Evaluation of Smear Removability>

(1) Substrate treatment of the built-in substrate

As the inner-layer substrate, a glass cloth-based epoxy resin double-sided copper clad laminate having a copper foil on the surface (copper foil thickness of 18 µm, substrate thickness of 0.8 mm, "R1515A" manufactured by Panasonic Corporation) was prepared. The copper foil of the surface of this inner-layer board|substrate was etched by 1 micrometer of copper etching amount using a micro-etching agent ("CZ8101" by Mack Corporation), and roughening process was performed. Thereafter, drying was performed at 190° C. for 30 minutes.

(2) Lamination and curing of resin sheets

The resin sheet produced in Production Example 1 was placed on both sides of the inner-layer substrate so that the resin composition layer was bonded to the inner-layer substrate using a batch vacuum pressurization laminator (2-stage build-up laminator “CVP700” manufactured by Nikko Materials Co., Ltd.). laminated. This lamination was performed by pressure-reducing for 30 second and making atmospheric|air pressure 13 hPa or less, and then crimping|bonding at a temperature of 100 degreeC, and pressure of 0.74 MPa for 30 second. Next, the laminated resin sheet was smoothed by hot pressing under atmospheric pressure at 100°C and at a pressure of 0.5 MPa for 60 seconds. Furthermore, this was put into an oven at 100°C and heated for 30 minutes, then transferred to an oven at 170°C and heated for 30 minutes. Thereby, the insulating layer formed of the hardened|cured material of the resin composition was formed.

(3) via hole formation:

Using a CO ₂ laser processing machine (LK-2K212/2C) manufactured by Via Mechanics, the insulating layer on one side of the inner-layer substrate is processed at a frequency of 2000 Hz, with a pulse width of 3 μsec, an output of 0.95 W, and a number of shots of 3 Thus, a via hole having a top diameter (diameter) of 50 µm on the surface of the insulating layer and a diameter of 50 µm on the bottom surface of the insulating layer was formed. Moreover, the support body was peeled after that, and the circuit board was obtained.

(4) Harmonization processing

The surface of the insulating layer of the circuit board was immersed in Swelling Deep Securigant P by Atotech Japan which is a swelling liquid at 60°C for 10 minutes. Next, the surface of the insulating layer of the circuit board was immersed in Atotech Japan's Concentrate Compact P (KMnO ₄ : 60 g/L, NaOH: 40 g/L aqueous solution) as a roughening liquid at 80°C for 25 minutes. Finally, the surface of the insulating layer of the circuit board was immersed in Atotech Japan's reduction solution Securigant P, which is a neutralizing solution, at 40°C for 5 minutes.

(5) Evaluation of residues at the bottom of the via hole

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

Evaluation standard

"○": The maximum smear length is less than 5 µm (that is, none of the three via holes has a smear length of 5 µm or more, and the smear removability is good)

"x": the maximum smear length is 5 µm or more (that is, at least one of the three via holes has a smear length of 5 µm or more, and the smear removability is poor)

<Test Example 3: Measurement and Evaluation of Elongation at Break>

Evaluation of softness was performed by measuring the elongation at break in the following procedure. With respect to the cured product A for evaluation, in accordance with Japanese Industrial Standards JIS K7127, a tensile test was performed with a Tenshiron universal testing machine (“RTC-1250A” manufactured by Orientec Co., Ltd.), and the elongation at break (%) was measured. Therefore, it evaluated by the following evaluation criteria.

Evaluation standard

「○」: Elongation at break is 1.0% or more

「×」: Elongation at break is less than 1.0%

The content of the nonvolatile component of the resin compositions of Examples and Comparative Examples, and the measurement results and evaluation results of Test Examples are shown in Table 1 below.

As shown in Table 1, (A) epoxy resin, (B) active ester compound, and (C) inorganic filler are included, (A) component contains (A-1) specific epoxy resin demonstrated above It can be seen that a cured product having a low dielectric loss tangent and excellent smear removability and elongation at break can be obtained by using the resin composition.

Claims (15)

A resin composition comprising (A) an epoxy resin, (B) an active ester compound, and (C) an inorganic filler, comprising:
(A) component, (A-1) formula (1):

[In formula (1),
R ¹ each independently represents a hydrogen atom, a group represented by the formula (1a), or a group represented by the formula (1b), and at least one R ¹ is a group represented by the formula (1a), or the formula is the group represented by (1b):

(In formulas (1a) and (1b), * represents a binding site.);
R ² and R ³ each independently represent a hydrocarbon group having 1 to 8 carbon atoms;
n is an integer of 0 or more and represents the number of repeating units.]
A resin composition for forming an interlayer insulating layer of a printed wiring board, comprising an epoxy resin represented by . The resin composition for forming an interlayer insulating layer of a printed wiring board according to claim 1, wherein the average value of n is in the range of 0 to 5. The resin composition for forming an interlayer insulating layer of a printed wiring board according to claim 1, wherein the component (A) further contains a liquid epoxy resin at a temperature of 20°C or lower. The resin composition for forming an interlayer insulating layer of a printed wiring board according to claim 1, wherein the content of the component (A) is 1% by mass to 30% by mass when the nonvolatile component in the resin composition is 100% by mass. The resin composition for forming an interlayer insulating layer of a printed wiring board according to claim 1, wherein the content of the component (B) is 5% by mass or more when the nonvolatile component in the resin composition is 100% by mass. The resin composition for forming an interlayer insulating layer of a printed wiring board according to claim 1, wherein the component (C) is silica. The resin composition for forming an interlayer insulating layer of a printed wiring board according to claim 1, wherein the content of the component (C) is 40% by mass or more when the nonvolatile component in the resin composition is 100% by mass. The resin composition for forming an interlayer insulating layer of a printed wiring board according to claim 1, further comprising a phenoxy resin. The resin composition for forming an interlayer insulating layer of a printed wiring board according to claim 1, further comprising a phenol-based curing agent. The resin composition for forming an interlayer insulating layer of a printed wiring board according to claim 1, wherein the elongation at break of the cured product of the resin composition is 1.0% or more when measured at 23°C according to JIS K7127. The resin composition for forming an interlayer insulating layer of a printed wiring board according to claim 1, wherein the dielectric loss tangent (Df) of the cured product of the resin composition is 0.0040 or less when measured at 5.8 GHz and 23°C. The resin composition for forming an interlayer insulating layer of a printed wiring board according to claim 1, wherein the dielectric constant (Dk) of the cured product of the resin composition is 3.5 or less when measured at 5.8 GHz and 23°C. A resin sheet having a support and a resin composition layer provided on the support, comprising:
The resin composition layer contains (A) an epoxy resin, (B) an active ester compound, and (C) an inorganic filler,
(A) component, (A-1) formula (1):

[In formula (1),
R ¹ each independently represents a hydrogen atom, a group represented by the formula (1a), or a group represented by the formula (1b), and at least one R ¹ is a group represented by the formula (1a), or the formula is the group represented by (1b):

(In formulas (1a) and (1b), * represents a binding site.);
R ² and R ³ each independently represent a hydrocarbon group having 1 to 8 carbon atoms;
n is an integer of 0 or more and represents the number of repeating units.]
A resin sheet for forming an interlayer insulating layer of a printed wiring board, which is a resin composition layer formed of a resin composition containing an epoxy resin represented by . A resin composition comprising (A) an epoxy resin, (B) an active ester compound, and (C) an inorganic filler, comprising:
(A) component, (A-1) formula (1):

[In formula (1),
R ¹ each independently represents a hydrogen atom, a group represented by the formula (1a), or a group represented by the formula (1b), and at least one R ¹ is a group represented by the formula (1a), or the formula A group represented by (1b) is:

(In formulas (1a) and (1b), * represents a binding site.);
R ² and R ³ each independently represent a hydrocarbon group having 1 to 8 carbon atoms;
n is an integer of 0 or more and represents the number of repeating units.]
A printed wiring board comprising an insulating layer made of a cured product of a resin composition containing an epoxy resin represented by . A semiconductor device comprising the printed wiring board according to claim 14 .