JP2023067521A - resin composition - Google Patents

Abstract

To provide a novel resin composition containing an active ester curing agent and capable of producing a cured product exhibiting good mechanical properties.SOLUTION: A resin composition includes (A) a thermosetting resin, (B) an active ester curing agent, and (C) a substituted pyridine compound in which a substituent aliphatic carbon or aromatic carbon is bonded to a pyridine ring.SELECTED DRAWING: None

Description

The present invention relates to resin compositions. Furthermore, it relates to a resin sheet, a cured product, a printed wiring board, a semiconductor chip package, and a semiconductor device using the resin composition.

A resin composition containing a thermosetting resin such as an epoxy resin and its curing agent provides a cured product with excellent insulation, heat resistance, adhesion, etc. Therefore, it is used for insulation of electronic parts such as printed wiring boards and semiconductor chip packages. widely used as a material.

On the other hand, with the increasing speed of communication in recent years, insulating materials with excellent dielectric properties (low dielectric constant, low dielectric loss tangent) are becoming more popular as insulating materials for electronic parts in order to reduce transmission loss when operating in high-frequency environments. is necessary. As an insulating material having excellent dielectric properties, for example, Patent Document 1 discloses a resin composition using an active ester curing agent as a curing agent.

JP 2009-235165 A

As electronic components become smaller and more functional, insulation materials become thinner and cracks are more likely to occur. In order to prevent this, insulating materials are required to have excellent mechanical properties, specifically high elongation at break. In this regard, the resin composition containing an active ester curing agent, such as the resin composition described in Patent Document 1, has the problem that the resulting cured product is hard and brittle, and cracks are likely to occur.

An object of the present invention is to provide a novel resin composition which contains an active ester curing agent and which can give a cured product exhibiting good mechanical properties.

As a result of intensive studies, the present inventors have found that the above problems can be solved by using a combination of specific substituted pyridine compounds, and have completed the present invention.

That is, the present invention includes the following contents.
[1] A resin composition containing (A) a thermosetting resin, (B) an active ester curing agent, and (C) a substituted pyridine compound in which a substituent aliphatic carbon or aromatic carbon is bonded to a pyridine ring.
[2] The resin composition according to [1], wherein the substituent in component (C) is a monovalent organic group containing an aromatic ring.
[3] According to [1] or [2], wherein in component (C), the substituent is one or more selected from the group consisting of aryl groups, heteroaryl groups, arylalkyl groups and heteroarylalkyl groups. of the resin composition.
[4] The resin composition according to any one of [1] to [3], wherein component (C) is a substituted pyridine compound having a substituent at the 4-position.
[5] The resin composition according to any one of [1] to [4], wherein the mass ratio of component (B) to component (A) (component (B)/component (A)) is 0.8 or more. thing.
[6] The resin according to any one of [1] to [5], wherein the content of component (C) is 0.1% by mass or more when the resin component in the resin composition is 100% by mass. Composition.
[7] The resin composition according to any one of [1] to [6], further comprising (D) an inorganic filler.
[8] The resin composition according to [7], wherein the content of component (D) is 50% by mass or more when the non-volatile component in the resin composition is 100% by mass.
[9] The resin composition according to any one of [1] to [8], wherein the cured product has an elongation at break of 1.5% or more.
[10] The resin composition according to any one of [1] to [9], which is used for insulating layers of printed wiring boards.
[11] The resin composition according to any one of [1] to [9], which is used for semiconductor encapsulation.
[12] A resin sheet comprising a support and a layer of the resin composition according to any one of [1] to [11] provided on the support.
[13] The resin sheet of [12], wherein the support is a thermoplastic resin film or metal foil.
[14] A cured product of the resin composition according to any one of [1] to [11].
[15] A printed wiring board comprising an insulating layer made of a cured product of the resin composition according to any one of [1] to [10].
[16] A semiconductor chip package comprising a sealing layer made of a cured resin composition according to any one of [1] to [9] and [11].
[17] A semiconductor device comprising the printed wiring board of [15] or the semiconductor chip package of [16].

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a novel resin composition that contains an active ester curing agent and that can provide a cured product exhibiting good mechanical properties.

<Description of terms>
As used herein, the term "aromatic ring" means a ring according to Hückel's rule in which the number of electrons contained in the π-electron system on the ring is 4p+2 (p is a natural number), a monocyclic aromatic ring, and It includes fused polycyclic aromatic rings in which two or more monocyclic aromatic rings are fused. The aromatic ring is an aromatic carbocyclic ring having only carbon atoms as ring-constituting atoms, or an aromatic heterocyclic ring having heteroatoms such as oxygen, nitrogen and sulfur atoms in addition to carbon atoms as ring-constituting atoms. obtain. In the present specification, unless otherwise specified, the number of carbon atoms in the aromatic ring is preferably 3 or more, more preferably 4 or more or 5 or more, still more preferably 6 or more, and the upper limit is preferably 24 or less, It is more preferably 18 or less or 14 or less, and still more preferably 10 or less. Examples of aromatic rings include monocyclic rings such as benzene ring, furan ring, thiophene ring, pyrrole ring, pyrazole ring, oxazole ring, isoxazole ring, thiazole ring, imidazole ring, pyridine ring, pyridazine ring, pyrimidine ring, and pyrazine ring. Formula aromatic ring: naphthalene ring, anthracene ring, phenanthrene ring, benzofuran ring, isobenzofuran ring, indole ring, isoindole ring, benzothiophene ring, benzimidazole ring, indazole ring, benzoxazole ring, benzoisoxazole ring, benzothiazole ring , a quinoline ring, an isoquinoline ring, a quinoxaline ring, an acridine ring, a quinazoline ring, a cinnoline ring, a phthalazine ring, and the like.

As used herein, the term "organic group" refers to a group containing at least carbon atoms as backbone atoms and may be linear, branched or cyclic. In the present specification, unless otherwise specified, the number of skeletal atoms of the organic group is preferably 1 to 100, more preferably 1 to 80, even more preferably 1 to 60, still more preferably 1 to 50, particularly preferably 1-30 or 1-20. Examples of organic groups include groups composed of one or more skeleton atoms (including at least carbon atoms) selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms.

As used herein, the term “C _p to C _q ” (where p and q are positive integers and satisfies p<q) means that the number of carbon atoms in the organic group described immediately after this term is p ~q. For example, "C ₁ -C ₁₂ alkyl group" refers to an alkyl group having 1 to 12 carbon atoms, and "C ₆ -C ₁₀ aryl-C ₁ -C ₆ alkyl group" refers to an alkyl group in which the number of carbon atoms in the aryl portion is 6 to 10, and an arylalkyl group having 1 to 6 carbon atoms in the alkyl portion.

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will now be described in detail with reference to its preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and can be arbitrarily modified without departing from the scope of the claims of the present invention and their equivalents.

[Resin composition]
The resin composition of the present invention comprises (A) a thermosetting resin, (B) an active ester curing agent, and (C) a substituted pyridine compound in which a substituent aliphatic carbon or aromatic carbon is bonded to a pyridine ring. It is characterized by

<(A) Thermosetting resin>
The resin composition of the present invention contains a thermosetting resin as component (A).

Examples of thermosetting resins include epoxy resins, benzocyclobutene resins, epoxy acrylate resins, urethane acrylate resins, urethane resins, cyanate resins, polyimide resins, benzoxazine resins, unsaturated polyester resins, phenol resins, melamine resins, and silicone resins. resins, phenoxy resins, and the like. Thermosetting resins may be used singly or in combination of two or more.

Among them, the thermosetting resin preferably contains an epoxy resin from the viewpoint of being able to provide a cured product having good dielectric properties and conductor adhesion in combination with the component (B) described below.

Examples of epoxy resins include bisphenol type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, and naphthalene type epoxy resin. , naphthol-type epoxy resin, anthracene-type epoxy resin, glycidylamine-type epoxy resin, glycidyl ester-type epoxy resin, cresol novolac-type epoxy resin, biphenyl-type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic formula 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. . Bisphenol-type epoxy resins refer to epoxy resins having a bisphenol structure, and include, for example, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, bisphenol S-type epoxy resins, and bisphenol AF-type epoxy resins. A biphenyl-type epoxy resin refers to an epoxy resin having a biphenyl structure, where the biphenyl structure may have a substituent such as an alkyl group, an alkoxy group, or an aryl group. Therefore, bixylenol type epoxy resins and biphenyl aralkyl type epoxy resins are also included in biphenyl type epoxy resins. Epoxy resins may be used singly or in combination of two or more.

As the epoxy resin, an aromatic epoxy resin is preferable. Here, the aromatic epoxy resin means an epoxy resin having an aromatic ring in its molecule.

The epoxy resin preferably has two or more epoxy groups in one molecule. When the non-volatile component of the epoxy resin is 100% by mass, the proportion of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass. % by mass or more.

Epoxy resins include epoxy resins that are liquid at a temperature of 20° C. (hereinafter referred to as “liquid epoxy resins”) and epoxy resins that are solid at a temperature of 20° C. (hereinafter referred to as “solid epoxy resins”).

A liquid epoxy resin having two or more epoxy groups in one molecule is preferable as the liquid epoxy resin.

Examples of liquid epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolak type epoxy resin, ester skeleton. cyclohexane-type epoxy resins, cyclohexanedimethanol-type epoxy resins, and epoxy resins having a butadiene structure are preferable.

Specific examples of liquid epoxy resins include "HP-4032", "HP-4032D", and "HP-4032SS" (naphthalene-type epoxy resins) manufactured by DIC Corporation; "828US" and "jER828EL" manufactured by Mitsubishi Chemical Corporation; "825", "Epikote 828EL" (bisphenol A type epoxy resin); "jER807", "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" manufactured by Mitsubishi Chemical Corporation (phenol novolak type epoxy resin ); "630" and "630LSD" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ZX1059" manufactured by Nippon Steel Chemical & Materials (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX; "Celoxide 2021P" manufactured by Daicel (alicyclic epoxy resin having an ester skeleton); "PB-3600" manufactured by Daicel (butadiene Epoxy resin having a structure); “ZX1658” and “ZX1658GS” (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nippon Steel Chemical & Materials Co., Ltd., and the like.

The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups per molecule, more preferably an aromatic solid epoxy resin having 3 or more epoxy groups per molecule.

Solid epoxy resins include bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, and tetraphenylethane type epoxy resin.

Specific examples of solid epoxy resins include "HP-4032H" (naphthalene type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" manufactured by DIC (naphthalene type tetrafunctional epoxy resin); DIC's "N-690" (cresol novolak type epoxy resin); DIC's "N-695" (cresol novolac type epoxy resin); DIC's "HP-7200HH", "HP-7200H", "HP-7200" (dicyclopentadiene type epoxy resin); DIC's "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" "(naphthylene ether type epoxy resin); Nippon Kayaku Co., Ltd. "EPPN-502H" (trisphenol type epoxy resin); Nippon Kayaku Co., Ltd. "NC7000L" (naphthol novolac type epoxy resin); Nippon Kayaku Co., Ltd. "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd. "ESN475V" (naphthol type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd. "ESN485" (naphthol novolac type epoxy resin); "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical; "YX4000HK" (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical; Mitsubishi Chemical Co., Ltd. "YX8800" (anthracene type epoxy resin); Osaka Gas Chemicals Co., Ltd. "PG-100", "CG-500"; Mitsubishi Chemical Co., Ltd. "YL7760" (bisphenol AF type epoxy resin); Mitsubishi "YL7800" (fluorene type epoxy resin) manufactured by Chemical Company; "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation, etc. mentioned.

As the epoxy resin, the resin composition of the present invention may contain only a liquid epoxy resin, may contain only a solid epoxy resin, or may contain a combination of a liquid epoxy resin and a solid epoxy resin. When a liquid epoxy resin and a solid epoxy resin are used in combination, the ratio by mass (liquid epoxy resin:solid epoxy resin) is preferably 1:0.01 to 1:50, more preferably 1:0.01 to 1:50. 1:0.05 to 1:20, more preferably 1:0.1 to 1:10.

The epoxy equivalent of the epoxy resin is preferably 50 g/eq. ~5000g/eq. , more preferably 50 g/eq. ~3000g/eq. , more preferably 80 g/eq. ~2000g/eq. , even more preferably 110 g/eq. ~1000g/eq. is. Epoxy equivalent weight is the weight of an epoxy resin containing one equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

The weight average molecular weight (Mw) of the epoxy resin is preferably 100-5000, more preferably 250-3000, still more preferably 400-1500. The Mw of the epoxy resin can be measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.

In combination with components (B) and (C), which will be described later, a cured product with good dielectric properties and conductor adhesion can be obtained, and a cured product with excellent mechanical properties can be obtained. The content of component (A) in the composition is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 12% by mass or more when the resin component in the resin composition is 100% by mass. , 14% by mass or more, or 15% by mass or more. The upper limit of the content is not particularly limited, and may be determined depending on the properties required of the resin composition. In the present invention, the "resin component" referred to in the resin composition refers to a non-volatile component constituting the resin composition, excluding the inorganic filler described below.

In the resin composition of the present invention, the content of the epoxy resin is preferably 40% by mass or more, more preferably 50% by mass or more, and still more preferably 55% by mass, when the non-volatile component of component (A) is 100% by mass. % or more, 60 mass % or more, 65 mass % or more, or 70 mass % or more. The upper limit of the content of the epoxy resin in the component (A) is not particularly limited, and may be 100% by mass, but may be, for example, 95% by mass or less, or 90% by mass or less.

<(B) Active ester curing agent>
The resin composition of the present invention contains an active ester curing agent as component (B). The component (B) usually has the function of curing the resin composition by reacting with the component (A).

A compound having one or more active ester groups in one molecule can be used as the active ester curing agent. Among them, active ester curing agents include phenol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, etc., which have two or more ester groups with high reaction activity per molecule. Compounds are preferred. The active ester curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferred.

Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.

Examples of phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, Benzenetriol, dicyclopentadiene-type diphenol compound, phenol novolak, and the like. Here, the term "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

Preferred specific examples of the active ester curing agent include an active ester curing agent containing a dicyclopentadiene type diphenol structure, an active ester curing agent containing a naphthalene structure, an active ester curing agent containing an acetylated product of phenol novolak, and benzoyl of phenol novolak. and an active ester curing agent containing a compound. Among them, an active ester curing agent containing a naphthalene structure and an active ester curing agent containing a dicyclopentadiene type diphenol structure are more preferable. "Dicyclopentadiene-type diphenol structure" represents a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

Commercially available active ester compounds include "EXB9451", "EXB9460", "EXB9460S", "EXB-8000L", "EXB-8000L-65M" and "EXB-8000L-65M" as active ester compounds containing a dicyclopentadiene type diphenol structure. EXB-8000L-65TM", "HPC-8000L-65TM", "HPC-8000", "HPC-8000-65T", "HPC-8000H", "HPC-8000H-65TM", (manufactured by DIC); naphthalene "EXB-8100L-65T", "EXB-8150-60T", "EXB-8150-62T", "EXB-9416-70BK", "HPC-8150-60T", "HPC- 8150-62T" (manufactured by DIC Corporation); "EXB9401" (manufactured by DIC Corporation) as a phosphorous-containing active ester compound, "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound that is an acetylated product of phenol novolac, and phenol novolak. "YLH1026", "YLH1030" and "YLH1048" (manufactured by Mitsubishi Chemical Corporation) as active ester compounds that are benzoyl compounds of , and "PC1300-02-65MA" (Air Water Inc.) as an active ester compound containing a styryl group and a naphthalene structure. made) and the like.

As described above, a resin composition containing an active ester curing agent can provide a cured product with good dielectric properties (low dielectric constant, low dielectric loss tangent). From the viewpoint of being able to provide a cured product with excellent dielectric properties, the content of component (B) in the resin composition is preferably 5% by mass or more when the resin component in the resin composition is 100% by mass. More preferably 10% by mass or more, still more preferably 15% by mass or more or 20% by mass or more. Here, a resin composition containing an active ester curing agent as a curing agent can realize a cured product with good dielectric properties, but when the content is increased to the extent that excellent dielectric properties can be achieved, the cured product becomes hard and brittle. There is a problem that it is likely to result in a product, and therefore crack defects are likely to occur. On the other hand, according to the resin composition of the present invention containing the component (C) described later, even when the active ester curing agent is contained to the extent that excellent dielectric properties can be realized, curing exhibits good mechanical properties. can bring things. For example, the content of component (B) in the resin composition may be increased to 25% by mass or more, 30% by mass or more, 35% by mass or more, or 40% by mass or more. The upper limit of the content is not particularly limited, and may be determined depending on the properties required of the resin composition.

In the resin composition of the present invention, the mass ratio of component (B) to component (A) ((B) component/(A) component) is preferably 0.5 or more from the viewpoint of providing a cured product having excellent dielectric properties. , more preferably 0.6 or more, and still more preferably 0.8 or more. As described above, according to the resin composition of the present invention containing the component (C), which will be described later, even when the active ester curing agent is contained to the extent that excellent dielectric properties can be achieved, curing exhibits good mechanical properties. can bring things. For example, in the resin composition of the present invention, the mass ratio of component (B) to component (A) may be increased to 1 or more, 1.1 or more, or 1.2 or more. The upper limit of the mass ratio (component (B)/component (A)) may be, for example, 2 or less, 1.9 or less, or 1.8 or less.

<(C) Substituted Pyridine Compound in which Aliphatic or Aromatic Carbon Substituent is Bonded to Pyridine Ring>
The resin composition of the present invention includes, as the component (C), a substituted pyridine compound in which an aliphatic carbon or aromatic carbon substituent is bonded to a pyridine ring (hereinafter referred to as "substituted pyridine compound in which an aliphatic carbon/aromatic carbon is bonded ", or simply referred to as "substituted pyridine compound").

The substituted pyridine compound of component (C) is characterized in that an aliphatic carbon or aromatic carbon substituent is bonded to the pyridine ring. By containing such a substituted pyridine compound, the resin composition of the present invention can provide a cured product exhibiting good mechanical properties while containing an active ester curing agent.

In component (C), the substituent of the pyridine ring is not particularly limited as long as it contains an aliphatic carbon or aromatic carbon capable of bonding to the pyridine ring, and any organic group may be used. The number of carbon atoms in the substituent is preferably 1 or more, more preferably 3 or more, still more preferably 4 or more, 5 or more, or 6 or more, and the upper limit is preferably 100 or less, more preferably 80 or less, and further It is preferably 60 or less, 50 or less, 30 or less, or 20 or less.

Among them, in combination with the components (A) and (B), from the viewpoint that a cured product exhibiting even better mechanical properties can be obtained, the substituent of the pyridine ring in the component (C) is an aromatic ring. It is preferably a monovalent organic group containing

In component (C), when the substituent on the pyridine ring is a monovalent organic group containing an aromatic ring, the aromatic ring contained in the monovalent organic group is, as described above, a monocyclic aromatic ring, and , a condensed polycyclic aromatic ring in which two or more monocyclic aromatic rings are condensed. Moreover, the aromatic ring may be either an aromatic carbocyclic ring or an aromatic heterocyclic ring. Among them, in combination with components (A) and (B), the monovalent organic group is preferably aromatic carbon from the viewpoint of easily realizing a resin composition that provides a cured product exhibiting even better mechanical properties. Contains rings.

In addition, the monovalent organic group is not particularly limited as long as it contains the above aromatic ring, and as described above, one or more skeleton atoms selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms is a monovalent group consisting of 1 to 100, 1 to 50, 1 to 30, 1 to 20, 1 to 12) skeleton atoms. Among them, in combination with components (A) and (B), from the viewpoint of providing a cured product exhibiting even better mechanical properties, the monovalent organic group contains only carbon atoms as skeleton atoms other than aromatic rings. It is particularly preferred to include

Therefore, in a preferred embodiment, the substituent on the pyridine ring is a monovalent organic group containing only carbon atoms as skeleton atoms other than the aromatic ring, more preferably an aromatic carbocyclic ring. and containing only carbon atoms as skeleton atoms. Preferred ranges for the number of carbon atoms in the aromatic ring and the number of skeleton atoms in the organic group are as described above. From the viewpoint of providing a product, the number of carbon atoms in the monovalent organic group is preferably 3 or more, more preferably 4 or more, still more preferably 5 or more or 6 or more, and the upper limit is preferably 24 or less, more It is preferably 20 or less, more preferably 18 or less, 14 or less, 12 or less, or 10 or less.

From the viewpoint of providing a cured product exhibiting even better mechanical properties in combination with components (A) and (B), the substituents possessed by the pyridine ring in component (C) are aryl groups, heteroaryl groups, It is preferably one or more selected from the group consisting of arylalkyl groups and heteroarylalkyl groups.

An aryl group used as a substituent is a group obtained by removing one hydrogen atom from an aromatic ring from an aromatic hydrocarbon. When the substituent of the pyridine ring is an aryl group, the aromatic carbon of the aryl group is bonded to the pyridine ring. The aryl group used as a substituent preferably has 6 to 24 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 14 carbon atoms, and still more preferably 6 to 10 carbon atoms. The aryl group includes, for example, phenyl group, naphthyl group, and anthracenyl group. Among them, an aryl group having 6 to 10 carbon atoms (eg, phenyl group, naphthyl group) is preferable, and an aryl group having 6 carbon atoms (ie, phenyl group) is more preferable, from the viewpoint of being able to enjoy the effects of the present invention more. .

A heteroaryl group used as a substituent refers to a group obtained by removing one hydrogen atom on the aromatic heterocyclic ring from an aromatic compound containing the aromatic heterocyclic ring. When the substituent of the pyridine ring is a heteroaryl group, the aromatic carbon of the heteroaryl group is bonded to the pyridine ring. The heteroaryl group preferably has 3 to 21 carbon atoms, more preferably 3 to 15 carbon atoms, still more preferably 3 to 9 carbon atoms, and still more preferably 3 to 6 carbon atoms. Examples of the heteroaryl group include thienyl, pyrrolyl, furanyl, furyl, pyridyl, pyridazinyl, pyrimidyl, pyrazinyl, triazinyl, pyrrolidyl, piperidyl, quinolyl, and isoquinolyl groups. be done. Among them, from the viewpoint of being able to enjoy the effects of the present invention more, a heteroaryl group containing a nitrogen atom as a heteroatom is preferable, and a heteroaryl group containing one or two nitrogen atoms as a heteroatom is more preferable. Heteroaryl groups containing one nitrogen atom are more preferred.

In the arylalkyl group used as a substituent, the aryl portion preferably has 6 to 24 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 14 carbon atoms, and still more preferably 6 to 10 carbon atoms. is preferably 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 6 carbon atoms. When the substituent of the pyridine ring is an arylalkyl group, the aliphatic carbon of the arylalkyl group is bonded to the pyridine ring. The arylalkyl groups include, for example, phenyl-C ₁ -C ₁₂ alkyl groups, naphthyl-C ₁ -C ₁₂ alkyl groups, and anthracenyl-C ₁ -C ₁₂ alkyl groups. Among them, a phenyl-C ₁ to C ₁₂ alkyl group is preferable, a phenyl-C ₁ to C ₁₀ alkyl group is more preferable, and a phenyl-C ₁ to C ₆ alkyl group is further preferable, from the viewpoint of being able to enjoy the effects of the present invention more. preferable.

In the heteroarylalkyl group used as a substituent, the number of carbon atoms in the heteroaryl portion is preferably 3 to 21, more preferably 3 to 15, still more preferably 3 to 9, still more preferably 3 to 6, The number of carbon atoms in the alkyl portion is preferably 1-12, more preferably 1-10, still more preferably 1-6. Examples of the heteroarylalkyl group include heteroaryl-C ₁ to C ₁₂ alkyl groups, and the heteroaryl portion is preferably a heteroaryl group containing a nitrogen atom as a heteroatom, as described above, and one heteroatom. or a heteroaryl group containing two nitrogen atoms is more preferred, and a heteroaryl group containing one nitrogen atom as the heteroatom is even more preferred. Among them, heteroaryl (containing one nitrogen atom as a heteroatom) -C ₁ to C ₁₂ alkyl group is preferable, and heteroaryl (containing one nitrogen atom as a heteroatom -C ₁ -C ₁₀ alkyl groups are more preferred, and heteroaryl (containing one nitrogen atom as a heteroatom) -C ₁ -C ₆ alkyl groups are more preferred.

In component (C), the pyridine ring preferably has 1 to 3 substituents, more preferably 1 or 2 substituents, and even more preferably 1 substituent. The pyridine ring in component (C) preferably has a substituent at least at the 4-position from the viewpoint of providing a cured product exhibiting outstanding mechanical properties in combination with components (A) and (B). . Thus, in one embodiment, component (C) is a substituted pyridine compound having a substituent at the 4-position.

In a more preferred embodiment, component (C) is one or more selected from the group consisting of 4-arylpyridine, 4-heteroarylpyridine, 4-arylalkylpyridine and 4-heteroarylalkylpyridine, More preferably, it is one or more selected from the group consisting of 4-heteroarylpyridine and 4-arylalkylpyridine. In such preferred embodiments, preferred examples of the aryl group, heteroaryl group, arylalkyl group, and heteroarylalkyl group as substituents are as described above.

In one particularly preferred embodiment, component (C) is 4-(C ₃ -C ₅ heteroaryl[heteroatom is a nitrogen atom])pyridine and 4-(C ₆ -C ₁₀ aryl-C ₁ -C ₆ alkyl ) one or more selected from the group consisting of pyridine, more preferably the group consisting of 4-pyridylpyridine (preferably 4,4′-bipyridyl), 4-(phenylpropyl)pyridine, and 4-benzylpyridine It is one or more selected from.

From the viewpoint that the combination of components (A) and (B) can provide a cured product with excellent mechanical properties, the content of component (C) in the resin composition is When 100% by mass, preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, 0.15% by mass or more, 0.2% by mass or more, 0.25% by mass or more, or 0.3% by mass or more, preferably 2% by mass or less, more preferably 1.5% by mass or less, 1% by mass or less, 0.8% by mass or less, or 0.7% by mass or less, or 0.6% by mass or less.

<(D) Inorganic filler>
The resin composition of the present invention may further contain an inorganic filler as component (D). By including component (D), the coefficient of linear thermal expansion and dielectric loss tangent can be further reduced.

Materials for component (D) include, for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, and aluminum silicate. , aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, Titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate phosphate, and the like. Among these, silica is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. As silica, spherical silica is preferable. (D) Component may be used individually by 1 type, and may be used in combination of 2 or more type.

Commercially available products of component (D) include, for example, “UFP-30” manufactured by Denka Kagaku Kogyo; “SP60-05” and “SP507-05” manufactured by Nippon Steel Chemical &Materials; YC100C", "YA050C", "YA050C-MJE", "YA010C"; "UFP-30" manufactured by Denka; "Silfil NSS-3N", "Silfil NSS-4N", "Silfil NSS-5N" manufactured by Tokuyama "SC2500SQ", "SO-C4", "SO-C2", "SO-C1" manufactured by Admatechs; "DAW-03" and "FB-105FD" manufactured by Denka; Taiheiyo Cement Co., Ltd. "MGH-005"; "BA-S" manufactured by Nikki Shokubai Kasei Co., Ltd.;

The average particle size of component (D) is not particularly limited, but is preferably 10 µm or less, more preferably 5 µm or less, and still more preferably 3 µm or less, 2 µm or less, 1 µm or less, or 0.7 µm or less. The lower limit of the average particle diameter is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, and still more preferably 0.07 μm or more, 0.1 μm or more, or 0.2 μm or more. be. The average particle size of component (D) can be measured by a laser diffraction/scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is prepared on a volume basis using a laser diffraction/scattering type particle size distribution measuring device, and the median diameter can be used as the average particle size for measurement. A measurement sample can be obtained by weighing 100 mg of an inorganic filler and 10 g of methyl ethyl ketone in a vial and dispersing them with ultrasonic waves for 10 minutes. A measurement sample is measured using a laser diffraction particle size distribution measuring device, the wavelengths of the light source used are blue and red, the volume-based particle size distribution of the inorganic filler is measured by the flow cell method, and from the obtained particle size distribution The average particle diameter was calculated as the median diameter. Examples of the laser diffraction particle size distribution analyzer include "LA-960" manufactured by Horiba, Ltd., and the like.

Although the specific surface area of component (D) is not particularly limited, it is 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, or 3 m ^{2 .} /g or 5 m ² /g or more. The upper limit of the specific surface area is not particularly limited, but is preferably 100 m ² /g or less, more preferably 80 m ² /g or less, still more preferably 60 m ² /g or less, 50 m ² /g or less, or 40 m ² / g or less. The specific surface area of component (D) is calculated according to the BET method by allowing nitrogen gas to be adsorbed on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) and calculating the specific surface area using the BET multipoint method. obtained by doing

Component (D) is preferably surface-treated with a suitable surface-treating agent. Moisture resistance and dispersibility of component (D) can be enhanced by surface treatment. Examples of surface treatment agents include vinyl-based silane coupling agents, epoxy-based silane coupling agents, styryl-based silane coupling agents, (meth)acrylic-based silane coupling agents, amino-based silane coupling agents, and isocyanurate-based silanes. Silane coupling agents such as coupling agents, ureido-based silane coupling agents, mercapto-based silane coupling agents, isocyanate-based silane coupling agents, and acid anhydride-based silane coupling agents; methyltrimethoxysilane, phenyltrimethoxysilane, etc. non-silane coupling-alkoxysilane compounds; silazane compounds; The surface treatment agents may be used singly or in combination of two or more.

Examples of commercially available surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical Industry Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "SZ-31" ( hexamethyldisilazane) and the like.

From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment with the surface treatment agent is preferably within a predetermined range. Specifically, 100% by mass of the inorganic filler is preferably surface-treated with 0.2 to 5% by mass of a surface treatment agent.

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m ² or more, more preferably 0.1 mg/m ² or more, and more preferably 0.2 mg/m ² from the viewpoint of improving the dispersibility of the inorganic filler. The above is more preferable. On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin composition and the melt viscosity in the form of a sheet, it is preferably 1.0 mg/m ² or less, more preferably 0.8 mg/m ² or less, and 0.5 mg/m ^{2 or less} . More preferred are: The amount of carbon per unit surface area of component (D) can be measured after the surface-treated inorganic filler is washed with a solvent (eg, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with the surface treatment agent, and ultrasonic cleaning is performed at 25° C. for 5 minutes. After removing the supernatant liquid and drying the solid content, a carbon analyzer can be used to measure the amount of carbon per unit surface area of the inorganic filler. As a carbon analyzer, "EMIA-320V" manufactured by Horiba Ltd. can be used.

When the resin composition of the present invention contains component (D), the content of component (D) in the resin composition may be determined according to the properties required for the resin composition. When the non-volatile component of is 100% by mass, it is, for example, 40% by mass or more, preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 65% by mass or more or 70% by mass or more. Although the upper limit of the content of component (D) is not particularly limited, it can be, for example, 90% by mass or less, or 80% by mass or less.

<(E) Thermoplastic resin>
The resin composition of the present invention may further contain a thermoplastic resin as component (E).

Examples of thermoplastic resins include phenoxy resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyimide resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polycarbonate resins, polyether resins. Ether ketone resins and polyester resins can be mentioned. The thermoplastic resin may be used singly or in combination of two or more.

The polystyrene equivalent weight average molecular weight of the thermoplastic resin is preferably in the range of 8,000 to 70,000, more preferably in the range of 10,000 to 60,000, and even more preferably in the range of 20,000 to 60,000. The polystyrene equivalent weight average molecular weight of the thermoplastic resin is measured by a gel permeation chromatography (GPC) method. Specifically, the weight average molecular weight of the thermoplastic resin in terms of polystyrene is measured by LC-9A/RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P/K- manufactured by Showa Denko Co., Ltd. as a column. 804L/K-804L can be measured at a column temperature of 40° C. using chloroform or the like as a mobile phase, and can be calculated using a standard polystyrene calibration curve.

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

Examples of polyvinyl acetal resins include polyvinyl formal resins and polyvinyl butyral resins, and polyvinyl butyral resins are preferred. Specific examples of polyvinyl acetal resins include Denka Butyral 4000-2, Denka Butyral 5000-A, Denka Butyral 6000-C, and Denka Butyral 6000-EP manufactured by Denka Kogyo Co., Ltd. , S-lec BH series, BX series, KS series, BL series, BM series manufactured by Sekisui Chemical Co., Ltd., and the like.

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

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

Specific examples of the polyethersulfone resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd., and the like.

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

When the resin composition of the present invention contains component (E), the content of component (E) in the resin composition may be determined according to the properties required for the resin composition. When the resin component is 100% by mass, for example, it is 0.1% by mass or more, preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 3% by mass or more or 4% by mass or more. be. The upper limit of the content of component (E) is not particularly limited, but may be, for example, 20% by mass or less, 10% by mass or less, or 8% by mass or less.

<(F) Other curing agents>
The resin composition of the present invention may further contain a curing agent (hereinafter also referred to as “other curing agent”) other than the (B) component as the (F) component.

Component (F) includes, for example, phenol-based curing agents, naphthol-based curing agents, acid anhydride-based curing agents, cyanate ester-based curing agents, carbodiimide-based curing agents, and amine-based curing agents. (F) component may be used individually by 1 type, and may be used in combination of 2 or more type.

From the viewpoint of heat resistance and water resistance, the phenol-based curing agent and naphthol-based curing agent preferably have a novolac structure. From the viewpoint of adhesion to the conductor layer, nitrogen-containing phenolic curing agents and nitrogen-containing naphthol curing agents are preferred, and triazine skeleton-containing phenolic curing agents and triazine skeleton-containing naphthol curing agents are more preferred.

Specific examples of phenol-based curing agents and naphthol-based curing agents include, for example, “MEH-7700”, “MEH-7810”, “MEH-7851” and “MEH-8000H” manufactured by Meiwa Kasei; Nippon Kayaku Co., Ltd. "NHN", "CBN", "GPH" manufactured by Nippon Steel Chemical & Materials Co., Ltd. "SN-170", "SN-180", "SN-190", "SN-475", "SN-485" ”, “SN-495”, “SN-495V”, “SN-375”, “SN-395”; DIC “TD-2090”, “TD-2090-60M”, “LA-7052”, "LA-7054", "LA-1356", "LA-3018", "LA-3018-50P", "EXB-9500", "HPC-9500", "KA-1160", "KA-1163", "KA-1165"; "GDP-6115L", "GDP-6115H", "ELPC75" manufactured by Gunei Chemical Co., Ltd.;

Acid anhydride curing agents include curing agents having one or more acid anhydride groups in one molecule. Specific examples of acid anhydride curing agents include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, and hydrogenated methylnadic acid. anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trianhydride mellitic acid, 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), polymer-type acid anhydrides such as styrene/maleic acid resin obtained by copolymerizing styrene and maleic acid. Commercially available acid anhydride-based curing agents include "MH-700" manufactured by Shin Nippon Rika Co., Ltd., and the like.

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

Specific examples of carbodiimide-based curing agents include Nisshinbo Chemical Co., Ltd. Carbodilite (registered trademark) V-03 (carbodiimide group equivalent: 216 g/eq.), V-05 (carbodiimide group equivalent: 262 g/eq.), V- 07 (carbodiimide group equivalent: 200 g/eq.); V-09 (carbodiimide group equivalent: 200 g/eq.); Rhein Chemie Stabaxol (registered trademark) P (carbodiimide group equivalent: 302 g/eq.).

Amine-based curing agents include curing agents having one or more amino groups in one molecule, such as aliphatic amines, polyether amines, alicyclic amines, and aromatic amines. mentioned. Specific examples of amine-based curing agents include 4,4′-methylenebis(2,6-dimethylaniline), diphenyldiaminosulfone, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and 3,3′. -diaminodiphenyl sulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 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-diphenylmethane Diamine, 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, and the like. Commercially available amine-based curing agents may be used. Kayahard AS", "Epicure W" manufactured by Mitsubishi Chemical Co., Ltd., and the like.

When the resin composition of the present invention contains component (F), the content of component (F) in the resin composition may be determined according to the properties required for the resin composition. 100% by mass, for example, it is 0.1% by mass or more, preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 3% by mass or more. Although the upper limit of the content of component (F) is not particularly limited, it can be, for example, 20% by mass or less, 15% by mass or less, or 10% by mass or less.

As described above, the resin composition of the present invention contains an active ester curing agent, that is, component (B), from the viewpoint of providing a cured product having excellent dielectric properties. In the resin composition of the present invention, the content of component (B) is preferably 50% by mass or more, more preferably 60% by mass, when the total of non-volatile components of component (B) and component (F) is 100% by mass. % by mass or more, more preferably 70% by mass or more, 75% by mass or more, or 80% by mass or more. The upper limit of the content of component (B) in the sum of component (B) and component (F) is not particularly limited, and may be 100% by mass, for example, 95% by mass or less, 90% by mass or less may be

<(G) Radically polymerizable compound>
The resin composition of the present invention may further contain a radically polymerizable compound as the (G) component.

The type of the radically polymerizable compound is not particularly limited as long as it has one or more (preferably two or more) radically polymerizable unsaturated groups in one molecule. As the radically polymerizable compound, for example, one selected from maleimide group, vinyl group, allyl group, styryl group, vinylphenyl group, acryloyl group, methacryloyl group, fumaroyl group, and maleoyl group as the radically polymerizable unsaturated group. Resins having the above are mentioned. Among them, the component (G) is selected from the group consisting of maleimide resins, (meth)acrylic resins and styryl resins, from the viewpoint that in combination with the component (A), a cured product exhibiting even better dielectric properties can be obtained. It is preferable to include one or more of the

As the maleimide resin, as long as it has one or more (preferably two or more) maleimide groups (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl groups) in one molecule, is not particularly limited. Examples of maleimide resins include "BMI-3000J", "BMI-5000", "BMI-1400", "BMI-1500", "BMI-1700", and "BMI-689" (all of which are Co., Ltd.), a maleimide resin containing an aliphatic skeleton having 36 carbon atoms derived from dimer diamine; a maleimide resin containing an indane skeleton, described in the Japan Institute of Invention and Innovation Public Technical Report No. 2020-500211; 3000-70MT” (manufactured by Nippon Kayaku Co., Ltd.), “BMI-4000” (manufactured by Daiwa Kasei Co., Ltd.), “BMI-80” (manufactured by Keiai Kasei Co., Ltd.), etc. A maleimide resin containing a ring skeleton is mentioned.

The type of the (meth)acrylic resin is not particularly limited as long as it has one or more (preferably two or more) (meth)acryloyl groups in one molecule, and it may be a monomer or an oligomer. Here, the term "(meth)acryloyl group" is a generic term for acryloyl group and methacryloyl group. Examples of methacrylic resins include "A-DOG" (manufactured by Shin-Nakamura Chemical Co., Ltd.), "DCP-A" (manufactured by Kyoeisha Chemical Co., Ltd.), "NPDGA", "FM-400", "R-687", " (Meth)acrylic resins such as THE-330”, “PET-30”, and “DPHA” (all manufactured by Nippon Kayaku Co., Ltd.).

The styryl resin is not particularly limited as long as it has one or more (preferably two or more) styryl groups or vinylphenyl groups in one molecule, and may be a monomer or an oligomer. Examples of styryl resins include styryl resins such as "OPE-2St", "OPE-2St 1200", and "OPE-2St 2200" (all manufactured by Mitsubishi Gas Chemical Co., Ltd.).

When the resin composition of the present invention contains component (G), the content of component (G) in the resin composition may be determined according to the properties required for the resin composition. 100% by mass, for example, it is 0.1% by mass or more, preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 3% by mass or more. The upper limit of the content of component (G) is not particularly limited, but may be, for example, 20% by mass or less, 15% by mass or less, or 10% by mass or less.

<Optional additives>
The resin composition of the present invention may further contain optional additives. Such additives include, for example, rubber particles, polyamide fine particles, organic fillers such as silicone particles; radical polymerization initiators such as peroxide-based radical polymerization initiators and azo-based radical polymerization initiators; organic copper compounds; Organometallic compounds such as organozinc compounds and organocobalt compounds; coloring agents such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; prohibiting polymerization of hydroquinone, catechol, pyrogallol, phenothiazine, etc. Leveling agents such as silicone leveling agents and acrylic polymer leveling agents; Thickeners such as bentone and montmorillonite; Silicone antifoaming agents, acrylic antifoaming agents, fluorine antifoaming agents, vinyl resin antifoaming agents UV absorbers such as benzotriazole UV absorbers; Adhesion improvers such as urea silane; Antioxidants such as hindered phenol-based antioxidants; Fluorescent brighteners such as stilbene derivatives; Surfactants such as fluorine-based surfactants and silicone-based surfactants; Flame retardants such as acid ester compounds, phosphazene compounds, phosphinic acid compounds, red phosphorus), nitrogen flame retardants (e.g. melamine sulfate), halogen flame retardants, inorganic flame retardants (e.g. antimony trioxide); phosphate ester dispersion agent, polyoxyalkylene dispersant, acetylene dispersant, silicone dispersant, anionic dispersant, cationic dispersant; borate stabilizer, titanate stabilizer, aluminate stabilizer, zirconate Stabilizers such as system stabilizers, isocyanate stabilizers, carboxylic acid stabilizers, and carboxylic anhydride stabilizers. The content of such additives may be determined according to the properties required for the resin composition.

<Organic solvent>
The resin composition of the present invention may further contain an organic solvent as a volatile component. Examples of organic solvents include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ester solvents; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether; alcohol solvents such as methanol, ethanol, propanol, butanol, ethylene glycol; acetic acid 2- Ether ester solvents such as ethoxyethyl, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, and methyl methoxypropionate; Ester alcohol solvent; ether alcohol solvent such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, diethylene glycol monobutyl ether (butyl carbitol); N,N-dimethylformamide, N,N - Amide solvents such as dimethylacetamide and N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethylsulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatic carbonization such as hexane, cyclopentane, cyclohexane, and methylcyclohexane Hydrogen-based solvents; aromatic hydrocarbon-based solvents such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, and the like. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

The resin composition of the present invention can be, for example, placed in an arbitrary preparation container as component (A), component (B), component (C), and, if necessary, component (D), component (E), and component (F). , (G) component, other additives and organic solvent in any order and/or by adding and mixing part or all of them at the same time. Also, during the process of adding and mixing each component, the temperature can be set appropriately, and heating and/or cooling may be performed temporarily or over time. In addition, during or after the addition and mixing, the resin composition may be stirred or shaken using a stirring or shaking device such as a mixer to uniformly disperse. Moreover, simultaneously with stirring or shaking, defoaming may be performed under low pressure conditions such as vacuum.

As described above, the resin composition of the present invention containing component (C) can provide a cured product exhibiting good mechanical properties while containing an active ester curing agent. As a result, the resin composition of the present invention can realize a cured product having both excellent dielectric properties and good mechanical properties together with the excellent dielectric properties inherently exhibited by the active ester curing agent. Furthermore, the resin composition of the present invention containing a combination of components (A), (B) and (C) exhibits good conductor adhesion.

In one embodiment, the cured product of the resin composition of the present invention exhibits excellent mechanical properties (elongation at break). For example, when a tensile test is performed according to JIS K7127 as described in the section [Elongation at break] described later, the elongation at break of the cured product of the resin composition of the present invention is preferably 1.5. % or more, 1.6% or more, 1.8% or more, or 2% or more. Since the cured product of the resin composition of the present invention exhibits such an elongation at break, even when forming a thin insulating material, the occurrence of crack defects is suppressed and the crack resistance is excellent. Effective.

In one embodiment, the cured product of the resin composition of the present invention exhibits high conductor adhesion. For example, when the adhesive strength (peel strength) with the plated conductor layer is measured as described in the section [Adhesion with the plated conductor layer] described later, the adhesion strength is preferably 0.35 kgf / cm or more and 0 0.36 kgf/cm or more, 0.38 kgf/cm or more, 0.4 kgf/cm or more, 0.42 kgf/cm or more, 0.44 kgf/cm or more, or 0.45 kgf/cm or more.

As described above, the resin composition of the present invention provides a cured product exhibiting good mechanical properties while using an active ester curing agent (and thus achieving good dielectric properties). Therefore, the resin composition of the present invention can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (a resin composition for an insulating layer of a printed wiring board), and can be used for interlayer insulation of a printed wiring board. It can be used more preferably as a resin composition for forming a layer (resin composition for insulating interlayers of printed wiring boards). The resin composition of the present invention can also be suitably used when the printed wiring board is a component built-in circuit board. The resin composition of the present invention can also be suitably used as a resin composition for encapsulating a semiconductor chip (resin composition for semiconductor encapsulation), and as an insulating layer for forming a rewiring layer. can be suitably used as a resin composition for the rewiring layer (resin composition for the rewiring layer). The resin composition of the present invention can be used in a wide range of applications that require resin compositions, such as resin sheets, sheet-like laminated materials such as prepreg, solder resists, underfill materials, die bonding materials, hole-filling resins, and component-embedding resins. can be used for

[Sheet-like laminate material (resin sheet, prepreg)]
Although the resin composition of the present invention can be used as it is, it may be used in the form of a sheet-like laminated material containing the resin composition.

As the sheet-like laminate material, resin sheets and prepregs shown below are preferable.

In one embodiment, the resin sheet includes a support and a resin composition layer provided on the support (hereinafter simply referred to as "resin composition layer"), and the resin composition layer is the resin composition layer of the present invention. It is characterized by being formed from a resin composition of

The preferred thickness of the resin composition layer varies depending on the application, and may be appropriately determined according to the application. For example, the thickness of the resin composition layer is preferably 200 μm or less, more preferably 150 μm or less, 120 μm or less, 100 μm or less, 80 μm or less, 60 μm or less, or 50 μm or less from the viewpoint of thinning printed wiring boards and semiconductor chip packages. is. Although the lower limit of the thickness of the resin composition layer is not particularly limited, it can be usually 1 μm or more, 5 μm or more, or the like.

Examples of the support include thermoplastic resin films, metal foils, and release papers, with thermoplastic resin films and metal foils being preferred. In one preferred embodiment, the support is therefore a thermoplastic film or a metal foil.

When a thermoplastic resin film is used as the support, examples of the thermoplastic resin include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), acrylics such as polycarbonate (PC) and polymethyl methacrylate (PMMA). , cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, and the like. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil, with copper foil being preferred. As the copper foil, a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. may be used.

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

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

When a metal foil is used as the support, a metal foil with a supporting substrate, which is obtained by laminating a peelable supporting substrate on a thin metal foil, may be used. In one embodiment, the metal foil with a supporting substrate includes a supporting substrate, a release layer provided on the supporting substrate, and a metal foil provided on the releasing layer. When a metal foil with a supporting base material is used as the support, the resin composition layer is provided on the metal foil.

In the metal foil with supporting substrate, the material of the supporting substrate is not particularly limited, and examples thereof include copper foil, aluminum foil, stainless steel foil, titanium foil, copper alloy foil and the like. When copper foil is used as the supporting substrate, it may be an electrolytic copper foil or a rolled copper foil. In addition, the release layer is not particularly limited as long as it can release the metal foil from the support base material, for example, Cr, Ni, Co, Fe, Mo, Ti, W, an alloy layer of an element selected from the group consisting of P; organic A film etc. are mentioned.

In the metal foil with a supporting substrate, for example, copper foil and copper alloy foil are preferable as the material of the metal foil.

In the metal foil with a supporting substrate, the thickness of the supporting substrate is not particularly limited, but is preferably in the range of 10 μm to 150 μm, more preferably in the range of 10 μm to 100 μm. Also, the thickness of the metal foil may be, for example, in the range of 0.1 μm to 10 μm.

In one embodiment, the resin sheet may further contain any layer as necessary. Examples of such an optional layer include a protective film provided on the surface of the resin composition layer that is not bonded to the support (that is, the surface opposite to the support). Although the thickness of the protective film is not particularly limited, it is, for example, 1 μm to 40 μm. By laminating the protective film, the surface of the resin composition layer can be prevented from being dusted or scratched.

The resin sheet is produced by, for example, using a liquid resin composition as it is or preparing a resin varnish by dissolving the resin composition in an organic solvent, coating it on a support using a die coater or the like, and drying it. It can be produced by forming a resin composition layer.

Examples of the organic solvent include the same organic solvents as those described as components of the resin composition. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

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

The resin sheet can be wound into a roll and stored. When the resin sheet has a protective film, it can be used by peeling off the protective film.

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

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

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

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

The sheet-like laminated material of the present invention can be suitably used for forming an insulating layer of a printed wiring board (for an insulating layer of a printed wiring board), and for forming an interlayer insulating layer of a printed wiring board (for a printed wiring board). for insulating interlayers of wiring boards). The sheet-like laminated material of the present invention can also be suitably used for sealing semiconductor chips (semiconductor sealing), and is used as an insulating layer for forming a rewiring layer. It can be used preferably.

[Printed wiring board]
The printed wiring board of the present invention includes an insulating layer made of a cured product of the resin composition of the present invention.

A printed wiring board can be manufactured, for example, using the above resin sheet by a method including the following steps (I) and (II).
(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) Curing (for example, thermosetting) the resin composition layer to form an insulating layer process

The "inner layer substrate" used in step (I) is a member that serves as a printed wiring board substrate, and includes, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. etc. The substrate may also have a conductor layer on one or both sides thereof, and the conductor layer may be patterned. An inner layer substrate having conductor layers (circuits) formed on one side or both sides of the substrate is sometimes referred to as an "inner layer circuit board." Further, an intermediate product on which an insulating layer and/or a conductor layer are to be further formed when manufacturing a printed wiring board is also included in the "inner layer substrate" as used in the present invention. When the printed wiring board is a circuit board with built-in components, an inner layer board with built-in components may be used.

The lamination of the inner layer substrate and the resin sheet can be performed, for example, by thermocompression bonding the resin sheet to the inner layer substrate from the support side. Examples of the member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter also referred to as "thermocompression bonding member") include heated metal plates (such as SUS end plates) and metal rolls (SUS rolls). The thermocompression member may be directly pressed onto the resin sheet, or may be pressed through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the uneven surface of the inner layer substrate.

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

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

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

The support may be removed between steps (I) and (II) or after step (II). When a metal foil is used as the support, the conductor layer may be formed using the metal foil without peeling off the support. Moreover, when a metal foil with a supporting substrate is used as the support, the supporting substrate (and the release layer) may be peeled off. And a conductor layer can be formed using metal foil.

In step (II), the resin composition layer is cured (for example, thermally cured) to form an insulating layer made of the cured resin composition. Curing conditions for the resin composition layer are not particularly limited, and conditions that are usually employed when forming an insulating layer of a printed wiring board may be used.

For example, although the thermosetting conditions for the resin composition layer vary depending on the type of resin composition, etc., in one embodiment, the curing temperature is preferably 140° C. to 250° C., more preferably 150° C. to 240° C., and even more preferably 150° C. to 240° C. is between 180°C and 230°C. The curing time can be preferably 5 minutes to 240 minutes, more preferably 10 minutes to 150 minutes, even more preferably 15 minutes to 120 minutes.

Before thermosetting the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermosetting the resin composition layer, the resin composition layer is cured at a temperature of 50° C. to 140° C., preferably 60° C. to 135° C., more preferably 70° C. to 130° C. for 5 minutes or more, It may be preheated for preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, even more preferably 15 minutes to 100 minutes.

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

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

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

Step (IV) is a step of roughening the insulating layer. Usually, removal of smear (desmear) is also performed in this step (IV). The procedure and conditions of the roughening treatment are not particularly limited, and known procedures and conditions that are commonly used in forming insulating layers of printed wiring boards can be employed. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralizing treatment with a neutralizing liquid in this order.

The swelling liquid used in the roughening treatment is not particularly limited, but examples thereof include alkaline solutions, surfactant solutions, etc., preferably alkaline solutions, more preferably sodium hydroxide solutions and potassium hydroxide solutions. preferable. Examples of commercially available swelling liquids include "Swelling Dip Securigans P" and "Swelling Dip Securigans SBU" manufactured by Atotech Japan. The swelling treatment with the swelling liquid is not particularly limited, but can be performed, for example, by immersing the insulating layer in the swelling liquid at 30.degree. C. to 90.degree. C. for 1 to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40° C. to 80° C. for 5 minutes to 15 minutes.

The oxidizing agent used in the roughening treatment is not particularly limited, but examples thereof include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated to 60° C. to 100° C. for 10 to 30 minutes. Further, the permanganate concentration in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Security P" manufactured by Atotech Japan.

Moreover, as a neutralization liquid used for the roughening treatment, an acidic aqueous solution is preferable, and as a commercial product, for example, "Reduction Solution Securigant P" manufactured by Atotech Japan Co., Ltd. can be mentioned.

The treatment with the neutralizing solution can be carried out by immersing the treated surface roughened with the oxidizing agent in the neutralizing solution at 30° C. to 80° C. for 5 to 30 minutes. From the viewpoint of workability, etc., a method of immersing an object roughened with an oxidizing agent in a neutralizing solution at 40° C. to 70° C. for 5 to 20 minutes is preferable.

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

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

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

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

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

In other embodiments, the conductor layer may be formed using a metal foil. When forming the conductor layer using a metal foil, step (V) is preferably performed between step (I) and step (II). For example, after step (I), the support is removed and a metal foil is laminated on the exposed surface of the resin composition layer. Lamination of the resin composition layer and the metal foil may be carried out by a vacuum lamination method. The lamination conditions may be the same as those described for step (I). Then, step (II) is performed to form an insulating layer. After that, using the metal foil on the insulating layer, a conductor layer having a desired wiring pattern can be formed by conventional known techniques such as the subtractive method and the modified semi-additive method.

A metal foil can be manufactured by a known method such as an electrolysis method or a rolling method. Commercially available metal foils include, for example, HLP foil and JXUT-III foil manufactured by JX Nippon Mining & Metals Co., Ltd., 3EC-III foil and TP-III foil manufactured by Mitsui Kinzoku Mining Co., Ltd., and the like.

Alternatively, as described above, when a metal foil or a metal foil with a supporting base material is used as the support for the resin sheet, the metal foil may be used to form the conductor layer.

[Semiconductor chip package]
The semiconductor chip package of the present invention includes a sealing layer made of a cured product of the resin composition of the present invention. As described above, the semiconductor chip package of the present invention may also include an insulating layer (rewiring forming layer) for forming a rewiring layer, which is made of a cured product of the resin composition of the present invention.

A semiconductor chip package can be produced, for example, using the resin composition and resin sheet of the present invention by a method including the following steps (1) to (6). The resin composition and resin sheet of the present invention may be used to form the sealing layer in step (3) or the rewiring layer in step (5). An example of forming a sealing layer or a rewiring forming layer using a resin composition or a resin sheet will be shown below. Then, using the resin composition and resin sheet of the present invention, a semiconductor package can be manufactured according to a known technique.
(1) a step of laminating a temporary fixing film on a substrate;
(2) temporarily fixing the semiconductor chip on the temporary fixing film;
(3) forming a sealing layer on the semiconductor chip;
(4) a step of peeling the base material and the temporary fixing film from the semiconductor chip;
(5) forming a rewiring layer as an insulating layer on the surface of the semiconductor chip from which the substrate and the temporary fixing film have been removed; and (6) forming a rewiring layer as a conductor layer on the rewiring layer. forming process

-Step (1)-
The material used for the base material is not particularly limited. Glass wafers; glass substrates; metal substrates such as copper, titanium, stainless steel, and cold-rolled steel plates (SPCC); 4 substrate); and a substrate made of bismaleimide triazine resin (BT resin).

The material of the temporary fixing film is not particularly limited as long as it can be peeled off from the semiconductor chip in step (4) and can temporarily fix the semiconductor chip. A commercially available product can be used as the temporary fixing film. Commercially available products include Riva Alpha manufactured by Nitto Denko Corporation.

-Step (2)-
Temporarily fixing the semiconductor chip can be performed using a known device such as a flip chip bonder and a die bonder. The layout and the number of arrangement of the semiconductor chips can be appropriately set according to the shape and size of the temporary fixing film, the production number of the target semiconductor package, etc. For example, a matrix of multiple rows and multiple columns can be aligned and temporarily fixed.

-Step (3)-
The resin composition layer of the resin sheet of the present invention is laminated on a semiconductor chip, or the resin composition of the present invention is applied onto a semiconductor chip and cured (for example, thermally cured) to form a sealing layer.

For example, lamination of a semiconductor chip and a resin sheet can be carried out by removing the protective film of the resin sheet and then heating and press-bonding the resin sheet to the semiconductor chip from the support side. Examples of the member for thermocompression bonding the resin sheet to the semiconductor chip (hereinafter also referred to as "thermocompression member") include a heated metal plate (such as a SUS panel) or a metal roll (SUS roll). Instead of directly pressing the thermocompression member against the resin sheet, it is preferable to press the resin sheet through an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently follow the unevenness of the surface of the semiconductor chip. The lamination of the semiconductor chip and the resin sheet may be carried out by a vacuum lamination method, and the lamination conditions are the same as the lamination conditions described in relation to the printed wiring board manufacturing method, and the preferred ranges are also the same.

After lamination, the resin composition is thermally cured to form a sealing layer. The heat curing conditions are the same as the heat curing conditions described in relation to the printed wiring board manufacturing method.

The support of the resin sheet may be peeled off after the resin sheet is laminated on the semiconductor chip and thermally cured, or the support may be peeled off before the resin sheet is laminated on the semiconductor chip.

When the resin composition of the present invention is applied to form a sealing layer, the application conditions are the same as those for forming the resin composition layer described in relation to the resin sheet of the present invention. , and the preferred ranges are also the same.

-Step (4)-
The method of peeling off the substrate and the temporary fixing film can be appropriately changed according to the material of the temporary fixing film. A method of exfoliating the temporary fixing film by irradiating it with ultraviolet rays from the side to reduce the adhesive force of the temporary fixing film.

In the method of heating and foaming (or expanding) the temporary fixing film to separate it, the heating conditions are usually 100 to 250° C. for 1 to 90 seconds or 5 to 15 minutes. In the method of removing the adhesive force of the temporary fixing film by irradiating it with ultraviolet rays from the substrate side, the irradiation dose of ultraviolet rays is usually 10 mJ/cm ² to 1000 mJ/cm ² .

-Step (5)-
The material for forming the rewiring layer (insulating layer) is not particularly limited as long as it has insulating properties when the rewiring layer (insulating layer) is formed. Ultraviolet curable resins and thermosetting resins are preferred. A rewiring formation layer may be formed using the resin composition and resin sheet of the present invention.

After forming the rewiring layer, a via hole may be formed in the rewiring layer in order to connect the semiconductor chip and a conductor layer to be described later. The via hole may be formed by a known method depending on the material of the rewiring formation layer.

-Step (6)-
The formation of the conductor layer on the rewiring formation layer may be carried out in the same manner as the step (V) described in relation to the printed wiring board manufacturing method. The steps (5) and (6) may be repeated to alternately build up the conductor layers (rewiring layers) and the rewiring formation layers (insulating layers).

In manufacturing a semiconductor chip package, (7) forming a solder resist layer on a conductor layer (rewiring layer), (8) forming bumps, (9) separating a plurality of semiconductor chip packages into individual semiconductor chips. A further step of dicing into packages and singulating may be performed. These steps may be performed according to various methods known to those skilled in the art for use in the manufacture of semiconductor chip packages.

By forming a sealing layer and a rewiring forming layer using the resin composition and resin sheet of the present invention, the semiconductor package is a fan-in type package or a fan-out type package. Regardless of whether it is a package or not, it is possible to realize a semiconductor chip package with extremely low transmission loss and suppressed occurrence of crack defects. In one embodiment, the semiconductor chip package of the present invention is a fan-out type package. The resin composition and resin sheet of the present invention can be applied to both fan-out panel level packages (FOPLP) and fan-out wafer level packages (FOWLP). In one embodiment, the semiconductor package of the present invention is a fan-out panel level package (FOPLP). In another embodiment, the semiconductor package of the present invention is a fan-out wafer level package (FOWLP).

[Semiconductor device]
The semiconductor device of the present invention includes a layer made of a cured product of the resin composition layer of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring board or semiconductor chip package of the present invention.

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

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

[Example 1. Preparation of resin composition 1]
Liquid epoxy resin (“ZX1059” manufactured by Nippon Steel Chemical & Materials Co., Ltd., 1:1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq) 5 parts, biphenyl type 15 parts of an epoxy resin ("NC3000H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 290) was dissolved in 20 parts of toluene and 20 parts of MEK while stirring. After cooling the resulting solution to room temperature, 40 parts of an active ester curing agent (manufactured by DIC "HPC-8000-65T", active group equivalent weight 223, solid content 65 mass% toluene solution), triazine skeleton-containing phenolic Curing agent ("LA-3018-50P" manufactured by DIC, hydroxyl equivalent of about 151 g / eq, 2-methoxypropanol solution with a solid content of 50%) 4 parts, phenoxy resin (manufactured by Mitsubishi Chemical "YX7553BH30", nonvolatile content 30 mass % MEK and cyclohexanone 1:1 solution) 10 parts, 4-(3-phenylpropyl) pyridine (solid content 5% MEK solution) 4 parts, inorganic filler (amine-based silane coupling agent (Shin-Etsu Chemical Co., Ltd. 150 parts of spherical silica (“SO-C2” manufactured by Admatechs, average particle size 0.5 μm)) surface-treated with “KBM573” manufactured by Admatechs Co., Ltd.) is mixed and uniformly dispersed with a high-speed rotating mixer to obtain resin composition 1. got

[Example 2. Preparation of resin composition 2]
A resin composition was prepared in the same manner as in Example 1, except that 6 parts of a carbodiimide curing agent (“V-03” manufactured by Nisshinbo Chemical Co., Ltd., an active group equivalent of about 216 g / eq, a toluene solution with a solid content of 50%) was added. got 2.

[Example 3. Preparation of resin composition 3]
Example 1 except that 4.3 parts of the MEK solution (solid content: 70% by mass) of maleimide compound 1 synthesized by the method described in Synthesis Example 1 of Invention Association Public Technical Report No. 2020-500211 was added. A resin composition 3 was obtained in the same manner.

[Example 4. Preparation of resin composition 4]
Active ester curing agent ("HPC-8000-65T" manufactured by DIC, active group equivalent 223 g / eq, solid content 65% by mass toluene solution) instead of 40 parts of active ester curing agent ("PC1300" manufactured by Air Water) A resin composition 4 was obtained in the same manner as in Example 1, except that 40 parts of methyl amyl ketone solution having an active group equivalent of 199 g/eq and a solid content of 65% by mass) was used.

[Example 5. Preparation of resin composition 5]
Same as Example 1, except that 4 parts of 4-(3-phenylpropyl)pyridine (5% solids MEK solution) were replaced with 4 parts 4-benzylpyridine (5% solids MEK solution). Then, a resin composition 5 was obtained.

[Example 6. Preparation of resin composition 6]
(1) 4-(3-phenylpropyl)pyridine (5% solids MEK solution) instead of 4 parts 4,4'-bipyridyl, 5% solids 1-methoxy-2-propanol solution) 4 parts (2) phenoxy resin (manufactured by Mitsubishi Chemical Corporation "YX7553BH30", 1:1 solution of MEK and cyclohexanone with a nonvolatile content of 30% by mass) 10 parts was not added. A resin composition 6 was obtained.

[Comparative Example 1. Preparation of comparative resin composition]
Same as Example 1, except that 4 parts of 4-dimethylaminopyridine (5% solids MEK solution) were used instead of 4 parts of 4-(3-phenylpropyl)pyridine (5% solids MEK solution). A comparative resin composition was obtained in the same manner.

[Production of resin sheet]
As a support, a polyethylene terephthalate film (“Lumirror R80” manufactured by Toray Industries, Inc., thickness 38 μm, softening point 130° C.) subjected to release treatment with an alkyd resin release agent (“AL-5” manufactured by Lintec) was prepared. .

Each of the resin compositions 1 to 6 and the comparative resin composition was uniformly coated on a support with a die coater so that the thickness of the resin composition layer after drying was 30 μm, and then coated at 70° C. to 95° C. for 3 times. By drying for minutes, a resin composition layer was formed on the support. Next, a rough surface of a polypropylene film (“Alphan MA-411” manufactured by Oji F-Tex Co., Ltd., thickness 15 μm) was attached as a protective film to the surface of the resin composition layer not bonded to the support. As a result, a resin sheet A having a support, a resin composition layer, and a protective film in this order was obtained.

[Adhesion to plated conductor layer]
(1) Preparation of inner layer substrate Glass cloth-based epoxy resin double-sided copper clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, Panasonic “R1515A”) on which the inner layer circuit is formed. The copper surface was roughened by etching by 1 μm with an etchant (“CZ8101” manufactured by MEC).

(2) Lamination of resin sheet The protective film was peeled off from the resin sheet A to expose the resin composition layer. Both surfaces of the inner layer substrate were laminated so that the resin composition layer was in contact with the inner layer substrate using a batch-type vacuum pressure laminator (manufactured by Nikko Materials Co., Ltd., 2-stage build-up laminator "CVP700"). Lamination was carried out by pressure bonding for 30 seconds at 120° C. and pressure of 0.74 MPa after reducing the pressure for 30 seconds to adjust the air pressure to 13 hPa or less. Then, hot pressing was performed at 100° C. and a pressure of 0.5 MPa for 60 seconds.

(3) Thermal curing of the resin composition layer After that, the inner layer substrate laminated with the resin sheet is placed in an oven at 130°C and heated for 30 minutes, then transferred to an oven at 180°C and heated for 30 minutes, The insulating layer was formed by thermally curing the resin composition layer. After that, the support was peeled off to obtain a cured substrate A having an insulating layer, an inner layer substrate and an insulating layer in this order.

(4) Roughening treatment The cured substrate A was subjected to a desmear treatment as a roughening treatment. As the desmear treatment, the following wet desmear treatment was performed.

(Wet desmear treatment)
The cured substrate A is immersed in a swelling liquid ("Swelling Dip Securigant P" manufactured by Atotech Japan Co., Ltd., an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60 ° C. for 5 minutes, and then an oxidizing agent solution (Atotech Japan company "Concentrate Compact CP", an aqueous solution with a potassium permanganate concentration of about 6% and a sodium hydroxide concentration of about 4%) at 80 ° C. for 20 minutes, then a neutralizing solution (Atotech Japan Co., Ltd. "Reduction Solution Securigant P", sulfuric acid aqueous solution) at 40°C for 5 minutes, and then dried at 80°C for 15 minutes.

(5) Formation of Conductor Layer A conductor layer was formed on the roughened surface of the insulating layer according to the semi-additive method. That is, the roughened substrate was immersed in an electroless plating solution containing PdCl ₂ at 40° C. for 5 minutes, and then immersed in an electroless copper plating solution at 25° C. for 20 minutes. Then, after annealing by heating at 150° C. for 30 minutes, an etching resist was formed and a pattern was formed by etching. Thereafter, copper sulfate electrolytic plating was performed to form a conductor layer having a thickness of 30 μm, and annealing treatment was performed at 200° C. for 60 minutes. The obtained substrate is called "evaluation substrate B".

(6) Evaluation of Adhesion to Plated Conductor Layer The peel strength between the insulating layer and the plated conductor layer was measured according to Japanese Industrial Standards (JIS C6481). Specifically, the conductor layer of evaluation board B was cut into a portion having a width of 10 mm and a length of 100 mm. The load (kgf/cm) was measured when 35 mm was peeled off to obtain the peel strength. A tensile tester ("AC-50C-SL" manufactured by TSE) was used for the measurement.

[Elongation at break]
The protective film was peeled off from the resin sheet A produced in Examples and Comparative Examples, and the resin composition layer was thermally cured by heating at 200° C. for 90 minutes, and then the support was peeled off. The resulting cured product is referred to as “evaluation cured product C”. The cured product C for evaluation was subjected to a tensile test according to Japanese Industrial Standards (JIS K7127) using a Tensilon universal testing machine (“RTC-1250A” manufactured by Orientec Co., Ltd.) to measure the elongation at break.

[Crack resistance]
(1) Resin sheet laminate Inner layer substrate having circuit conductors (copper) formed on both sides with a wiring pattern of L / S = 8 μm / 8 μm (manufactured by Hitachi Chemical Co., Ltd. “MCL-E700G”, conductor layer thickness 35 μm , a total thickness of 0.4 mm, and a residual copper content of 40%) were laminated with a resin sheet A from which the protective film was removed so that the resin composition layer was in contact with the inner layer substrate. Such lamination is performed using a vacuum pressure laminator ("MVLP-500" manufactured by Meiki Seisakusho Co., Ltd.), after vacuum suction for 30 seconds at a temperature of 120 ° C., under the conditions of a temperature of 120 ° C. and a pressure of 0.7 MPa, from the PET film. , and laminated by pressing for 30 seconds via a heat-resistant rubber. Next, under atmospheric pressure, pressing was performed for 60 seconds under conditions of a temperature of 120° C. and a pressure of 0.55 MPa using a SUS panel.

(2) Thermal curing of the resin composition layer After that, the inner layer substrate laminated with the resin sheet is placed in an oven at 130°C and heated for 30 minutes, then transferred to an oven at 180°C and heated for 30 minutes, The insulating layer was formed by thermally curing the resin composition layer. After that, the support was peeled off to obtain a cured substrate D having an insulating layer, an inner layer substrate and an insulating layer in this order.

(3) Roughening treatment The cured substrate D was subjected to a desmearing treatment as a roughening treatment. The desmear treatment was carried out in the same manner as the (wet desmear treatment) described in the above [Adhesion to plated conductor layer] column.

(4) Evaluation of Crack Resistance Among the insulating layer surfaces after the desmear treatment, the insulating layer surface immediately above the wiring pattern (L/S=8 μm/8 μm) of the inner layer substrate was observed. For 100 samples, it was confirmed whether or not cracks occurred on the surface of the insulating layer along the pattern shape of the inner layer substrate, and the percentage of samples without cracks was determined. This ratio was calculated as a "yield", and a yield of 50% or more was evaluated as "good", and a yield of less than 50% was evaluated as "poor".

Table 1 shows the results of Examples 1 to 6 and Comparative Example 1.

Claims (17)

A resin composition comprising (A) a thermosetting resin, (B) an active ester curing agent, and (C) a substituted pyridine compound in which a substituent aliphatic carbon or aromatic carbon is bonded to a pyridine ring. 2. The resin composition according to claim 1, wherein the substituent in component (C) is a monovalent organic group containing an aromatic ring. 3. The resin composition according to claim 1, wherein the substituent in component (C) is one or more selected from the group consisting of aryl groups, heteroaryl groups, arylalkyl groups and heteroarylalkyl groups. The resin composition according to any one of claims 1 to 3, wherein component (C) is a substituted pyridine compound having a substituent at the 4-position. The resin composition according to any one of claims 1 to 4, wherein the mass ratio of component (B) to component (A) (component (B)/component (A)) is 0.8 or more. The resin composition according to any one of claims 1 to 5, wherein the content of component (C) is 0.1% by mass or more when the resin component in the resin composition is taken as 100% by mass. The resin composition according to any one of claims 1 to 6, further comprising (D) an inorganic filler. 8. The resin composition according to claim 7, wherein the content of component (D) is 50% by mass or more based on 100% by mass of non-volatile components in the resin composition. The resin composition according to any one of claims 1 to 8, wherein the cured product has an elongation at break of 1.5% or more. The resin composition according to any one of claims 1 to 9, which is used for an insulating layer of a printed wiring board. The resin composition according to any one of claims 1 to 9, which is used for semiconductor encapsulation. A resin sheet comprising a support and a layer of the resin composition according to any one of claims 1 to 11 provided on the support. 13. The resin sheet according to claim 12, wherein the support is a thermoplastic resin film or metal foil. A cured product of the resin composition according to any one of claims 1 to 11. A printed wiring board comprising an insulating layer comprising a cured product of the resin composition according to any one of claims 1 to 10. A semiconductor chip package comprising a sealing layer comprising a cured product of the resin composition according to any one of claims 1 to 9 and 11. A semiconductor device comprising the printed wiring board according to claim 15 or the semiconductor chip package according to claim 16 .