Resin composition

Abstract

The present invention addresses the problem of providing: a resin composition capable of forming a cured product that exhibits good dielectric properties, while having excellent stain removal properties, and excellent adhesion strength with a conductor layer; a resin sheet comprising the resin composition; a circuit board comprising a cured product of the resin composition; and a semiconductor device including the circuit board. The present invention is a resin composition containing (A) an epoxy resin and (B) an active ester-based resin, the component (B) containing (B1) an active ester-based resin containing a specific structural unit and (B2) an active ester-based resin containing an allyl group.

Description

Technical Field

[0001] The present invention relates to a resin composition, a resin sheet, a circuit board, and a semiconductor device. Background Art

[0002] Since a resin composition containing an epoxy resin and its curing agent provides a cured product having excellent insulation properties, heat resistance, adhesion, etc., it is widely used as an insulating material for circuit boards such as printed wiring boards and rewiring substrates for semiconductor chip packages.

[0003] On the other hand, with the recent high-speedization of communication, in order to reduce transmission loss during operation in a high-frequency environment, the insulating material of a circuit board requires an insulating material having excellent dielectric properties (low dielectric loss tangent). As an insulating material having excellent dielectric properties, materials using specific curing agents such as active ester resins that can reduce or suppress the generation of polar groups such as secondary hydroxyl groups in the curing reaction of epoxy resins have been reported (for example, Patent Documents 1 and 2).

[0004] Prior Art Documents

[0005] Patent Documents

[0006] Patent Document 1: Japanese Patent No. 6205692 Gazette

[0007] Patent Document 2: Japanese Patent No. 7259783 Gazette Summary of the Invention

[0008] Problems to be Solved by the Invention

[0009] In this regard, when the active ester resin is blended to such an extent that good dielectric properties are achieved, there is a tendency for the stain removability during stain removal treatment to deteriorate. In addition, since the insulating layer of the circuit board is in contact with the conductor layer, good adhesion strength with the conductor layer (for example, copper foil as the base layer, copper plating) is required.

[0010] Therefore, an object of the present invention is to provide: a resin composition capable of forming a cured product that exhibits good dielectric properties, excellent stain removability, and excellent adhesion strength with a conductor layer; a resin sheet containing the resin composition; a circuit board containing a cured product of the resin composition; and a semiconductor device containing the circuit board.

[0011] Means for Solving the Problems

[0012] The present invention has been intensively studied to solve the above problems, and as a result, it has been found that in a resin composition containing (A) an epoxy resin and (B) an active ester resin, the above problems can be solved by including in the (B) component: (B1) an active ester resin containing a specific structural unit and (B2) an active ester resin containing an allyl group, thereby completing the present invention.

[0013] That is, the present invention includes the following.

[0014] <1>

[0015] A resin composition comprising: (A) an epoxy resin and (B) an active ester resin,

[0016] (The (B) component includes: (B1) an active ester resin containing a structural unit represented by the following formula (B1-1) and (B2) an active ester resin containing an allyl group,

[0017] [Chemical formula 1]

[0018]

[0019] In formula (B1-1),

[0020] Ar 1 Each independently represents a divalent aromatic group which may have a substituent;

[0021] At least one of the Ars 1 Is a naphthylene group which may have a substituent;

[0022] L B Each independently represents a single bond or a divalent linking group;

[0023] R B1 Represents a divalent hydrocarbon group which may have a substituent, an oxygen atom, a sulfur atom or a divalent group composed of a combination thereof;

[0024] m1 is an integer from 0 to 5;

[0025] "*" represents a bonding bond.

[0026] <2>

[0027] The resin composition according to <1>, wherein the quantitative ratio of the (A) component to the (B) component is in the range of 1:0.3 to 1:2 in terms of the ratio of [(total count of epoxy groups of the (A) component)]:[(total count of active ester groups of the (B) component)].

[0028] <3>

[0029] The resin composition according to <1> or <2>, wherein when the resin component in the resin composition is set to 100% by mass, the content of component (A) is 20% by mass or more and 50% by mass or less.

[0030] <4>

[0031] The resin composition according to any one of <1> to <3>, wherein when the resin component in the resin composition is set to 100% by mass, the content of component (B1) is 10% by mass or more and 60% by mass or less.

[0032] <5>

[0033] The resin composition according to any one of <1> to <4>, wherein when the resin component in the resin composition is set to 100% by mass, the content of component (B2) is 10% by mass or more and 60% by mass or less.

[0034] <6>

[0035] The resin composition according to any one of <1> to <5>, further comprising (C) an inorganic filler.

[0036] <7>

[0037] The resin composition according to <6>, wherein when the non-volatile component in the resin composition is set to 100% by mass, the content of component (C) is 50% by mass or more and 90% by mass or less.

[0038] <8>

[0039] The resin composition according to any one of <1> to <7> is used for forming an insulating layer.

[0040] <9>

[0041] A resin sheet having a support and a resin composition layer provided on the support,

[0042] The resin composition layer contains the resin composition according to any one of <1> to <8>.

[0043] <10>

[0044] A circuit board comprising a cured product of the resin composition according to any one of <1> to <8>.

[0045] <11>

[0046] A semiconductor device comprising the circuit board according to <10>.

[0047] Advantages of the Invention

[0048] According to the present invention, there can be provided: a resin composition capable of forming a cured product that exhibits good dielectric properties, excellent stain removability, and excellent adhesion strength to a conductor layer; a resin sheet containing the resin composition; a circuit board containing a cured product of the resin composition; and a semiconductor device including the circuit board. Detailed Description

[0049] <Explanation of Terms>

[0050] In the present specification, the term "may have a substituent" when referring to a compound or a group means both the case where the hydrogen atom of the compound or group is not substituted with a substituent and the case where a part or all of the hydrogen atoms of the compound or group are substituted with a substituent.

[0051] In the present specification, unless otherwise specified, the term "substituent" means a halogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, a monovalent heterocyclic group, an alkylidene group, an amino group, a silyl group, a carboxyl group, a sulfo group, a cyano group, a nitro group, a hydroxyl group, a mercapto group, and an oxo group.

[0052] Examples of the halogen atom used as a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkyl group used as a substituent may be either linear or branched. The number of carbon atoms of the alkyl group is preferably 1 to 12, more preferably 1 to 6, and further preferably 1 to 3. The alkenyl group used as a substituent may be either linear or branched. The number of carbon atoms of the alkenyl group is preferably 2 to 12, more preferably 2 to 6, and further preferably 2 or 3. The number of carbon atoms of the cycloalkyl group used as a substituent is preferably 3 to 12, more preferably 3 to 6. The alkoxy group used as a substituent may be either linear or branched. The number of carbon atoms of the alkoxy group is preferably 1 to 12, more preferably 1 to 6. The number of carbon atoms of the cycloalkoxy group used as a substituent is preferably 3 to 12, more preferably 3 to 6. The aryl group used as a substituent is a group obtained by removing one hydrogen atom from an aromatic ring of an aromatic hydrocarbon. The number of carbon atoms of the aryl group used as a substituent is preferably 6 to 14, more preferably 6 to 10. The number of carbon atoms of the aryloxy group used as a substituent is preferably 6 to 14, more preferably 6 to 10. The number of carbon atoms of the arylalkyl group used as a substituent is preferably 7 to 15, more preferably 7 to 11. The number of carbon atoms of the arylalkoxy group used as a substituent is preferably 7 to 15, more preferably 7 to 11. The monovalent heterocyclic group used as a substituent is a group obtained by removing one hydrogen atom from a heterocyclic ring of a heterocyclic compound. The number of carbon atoms of the monovalent heterocyclic group is preferably 3 to 15, more preferably 3 to 9. The alkylidene group used as a substituent is a group obtained by removing two hydrogen atoms from the same carbon atom of an alkane. The number of carbon atoms of the alkylidene group is preferably 1 to 12, more preferably 1 to 6, and further preferably 1 to 3. The above substituents may further have substituents (hereinafter sometimes referred to as "secondary substituents"). As the secondary substituents, the same substituents as those described above may be used unless otherwise specified.

[0053] In this specification, the term "aromatic group" refers to a group obtained by removing one hydrogen atom from an aromatic ring of an aromatic compound. Specifically, a monovalent aromatic group refers to a group obtained by removing one hydrogen atom from an aromatic ring of an aromatic compound, and a divalent aromatic group refers to a group obtained by removing two hydrogen atoms from an aromatic ring of an aromatic compound. In addition, the term "aromatic ring" means a ring that obeys Hückel's rule where the number of electrons contained in the π-electron system of the ring is 4n + 2 (n is a natural number), including a monocyclic aromatic ring and a fused aromatic ring formed by fusing two or more monocyclic aromatic rings. The aromatic ring can be a carbocyclic ring or a heterocyclic ring. Examples of the monovalent aromatic group include an aryl group that may have a substituent and a heteroaryl group that may have a substituent. Examples of the divalent aromatic group include an arylene group that may have a substituent and a heteroarylene group that may have a substituent. In this specification, unless otherwise specified, the number of carbon atoms of the aromatic group is preferably 3 or more, more preferably 4 or more or 5 or more, and further preferably 6 or more, and the upper limit is preferably 24 or less, more preferably 18 or less or 14 or less, and further preferably 10 or less. The number of carbon atoms does not include the number of carbon atoms of the substituent.

[0054] In this specification, the term "aliphatic group" refers to a group obtained by removing one or more hydrogen atoms bonded to an aliphatic carbon of an aliphatic compound. Specifically, a divalent aliphatic group refers to a group obtained by removing two hydrogen atoms bonded to an aliphatic carbon of an aliphatic compound. Examples of the divalent aliphatic group include an alkylene group that may have a substituent, a cycloalkylene group that may have a substituent, an alkenylene group that may have a substituent, a cycloalkenylene group that may have a substituent, and an alkapolyene group that may have a substituent (the number of double bonds is preferably 2 to 10, more preferably 2 to 6, further preferably 2 to 4, and further more preferably 2). In this specification, unless otherwise specified, the number of carbon atoms of the aliphatic group is preferably 1 or more, more preferably 2 or more, further preferably 3 or more, 4 or more, 5 or more or 6 or more, and preferably 50 or less, more preferably 40 or less, further preferably 30 or less, 20 or less, 18 or less, 16 or less, 14 or less or 12 or less. The number of carbon atoms does not include the number of carbon atoms of the substituent.

[0055] In this specification, the "non-volatile component" mentioned with respect to the resin composition refers to the components other than the organic solvent described below among the components constituting the resin composition. In addition, the "resin component" mentioned with respect to the resin composition refers to the components other than the inorganic filler described below among the non-volatile components constituting the resin composition.

[0056] Hereinafter, embodiments and examples are shown to explain the present invention in detail. However, the present invention is not limited to the following embodiments and examples and can be implemented with any changes within the scope of the claims of the present invention and their equivalents.

[0057] [Resin composition]

[0058] The resin composition of the present invention is characterized by comprising: (A) an epoxy resin and (B) an active ester resin, and the component (B) comprises: (B1) an active ester resin containing a structural unit represented by the formula (B1-1), and (B2) an active ester resin containing an allyl group.

[0059] As described above, in order to reduce the transmission loss during operation in a high-frequency environment, the insulating material of the circuit board needs to exhibit good dielectric properties. In this regard, the present inventors have found that when the active ester resin is blended to an extent that achieves good dielectric properties, the resulting insulating material tends to have poor stain removability during stain removal treatment.

[0060] In contrast, in the combination of an epoxy resin and an active ester resin, the present invention using an active ester resin containing a structural unit represented by the formula (B1-1) and an active ester resin containing an allyl group exhibits good dielectric properties and good stain removability. In addition, a cured product having excellent adhesion strength to the conductor layer can be formed. Thus, the present invention can provide a cured product that simultaneously exhibits good dielectric properties and good stain removability, and excellent adhesion strength to the conductor layer, which is advantageously used to reduce the transmission loss during operation in a high-frequency environment and significantly contributes to realizing a circuit board having a circuit that exhibits desired characteristics.

[0061] Hereinafter, each component will be described.

[0062] <(A) Epoxy resin>

[0063] The resin composition of the present invention contains an epoxy resin as the component (A).

[0064] Examples of the epoxy resin include bisphenol type epoxy resins, dicyclopentadiene type epoxy resins, triphenol type epoxy resins, naphthol novolak type epoxy resins, phenol novolak type epoxy resins, tert-butyl-catechol type epoxy resins, naphthalene type epoxy resins, naphthol type epoxy resins, anthracene type epoxy resins, glycidylamine type epoxy resins, glycidyl ester type epoxy resins, cresol novolak type epoxy resins, biphenyl type epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, epoxy resins containing a spiro ring, cyclohexane type epoxy resins, cyclohexanedimethanol type epoxy resins, naphthalene ether type epoxy resins, trimethylol type epoxy resins, and tetraphenylethane type epoxy resins. The bisphenol type epoxy resin refers to an epoxy resin having a bisphenol structure, and examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and bisphenol AF type epoxy resin. The biphenyl type epoxy resin refers to an epoxy resin having a biphenyl structure, and here, the biphenyl structure may have substituents such as an alkyl group, an alkoxy group, and an aryl group. Therefore, the xylenol type epoxy resin and the biphenyl aralkyl type epoxy resin are also included in the biphenyl type epoxy resin. The epoxy resin may be used alone or in combination of two or more kinds.

[0065] As the epoxy resin, an aromatic epoxy resin is preferred. Here, the aromatic epoxy resin means an epoxy resin having an aromatic ring in its molecule.

[0066] The epoxy resin preferably has two or more epoxy groups in one molecule. When 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, still more preferably 70% by mass or more, and usually 100% by mass or less.

[0067] The epoxy resin includes an epoxy resin that is liquid at 20°C (hereinafter referred to as "liquid epoxy resin") and an epoxy resin that is solid at 20°C (hereinafter referred to as "solid epoxy resin").

[0068] As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferred.

[0069] As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolak type epoxy resin, alicyclic epoxy resins such as alicyclic epoxy resins having an ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, and epoxy resin having a butadiene structure are preferred.

[0070] As specific examples of the liquid epoxy resin, the following can be cited: "HP-4032", "HP-4032-D", "HP-4032-SS" (naphthalene-type epoxy resin) manufactured by DIC Corporation; "828US", "jER828EL", "825", "Epikote828EL" (bisphenol A-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER807", "1750" (bisphenol F-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630", "630LSD" (glycidylamine-type epoxy resin) manufactured by Nippon Steel Chemical & Materials Co., Ltd.; "ZX1059" (a mixture of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin) manufactured by Nippon Steel Chemical & Materials Co., Ltd.; "EX-721" (glycidyl ester-type epoxy resin) manufactured by Nagase ChemteX Corporation; "Celloxide 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by Daicel Corporation; "PB-3600" (epoxy resin having a butadiene structure) manufactured by Daicel Corporation; "ZX1658", "ZX1658GS" (liquid 1,4-glycidylcyclohexane-type epoxy resin) manufactured by Nippon Steel Chemical & Materials Co., Ltd., etc.

[0071] As the solid epoxy resin, a solid epoxy resin having 3 or more epoxy groups in one molecule is preferred, and an aromatic solid epoxy resin having 3 or more epoxy groups in one molecule is more preferred.

[0072] As the solid epoxy resin, preferred are dimethylphenol-type epoxy resin, naphthalene-type epoxy resin, naphthalene tetrafunctional epoxy resin, cresol novolac-type epoxy resin, dicyclopentadiene-type epoxy resin, triphenol-type epoxy resin, naphthol-type epoxy resin, biphenyl-type epoxy resin, naphthalene ether-type epoxy resin, anthracene-type epoxy resin, bisphenol A-type epoxy resin, bisphenol AF-type epoxy resin, and tetraphenylethane-type epoxy resin.

[0073] As specific examples of the solid epoxy resin, the following can be cited: "HP-4032H" (naphthalene-type epoxy resin) manufactured by DIC Corporation; "HP-4700", "HP-4710" (tetrafunctional naphthalene-type epoxy resin) manufactured by DIC Corporation; "N-690" (cresol novolak-type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolak-type epoxy resin) manufactured by DIC Corporation; "HP-7200HH", "HP-7200H", "HP-7200" (dicyclopentadiene-type epoxy resin) manufactured by DIC Corporation; "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthalene ether-type epoxy resin) manufactured by DIC Corporation; "EPPN-502H" (triphenol-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC-7000L" (naphthol novolak-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC-3000H", "NC-3000", "NC-3000L", "NC-3100" (biphenyl-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "ESN-475V" (naphthol-type epoxy resin) manufactured by Nippon Steel Chemical & Materials Co., Ltd.; "ESN-485" (naphthol novolak-type epoxy resin) manufactured by Nippon Steel Chemical & Materials Co., Ltd.; "YX4000H", "YX4000", "YL6121" (biphenyl-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX4000HK" (xylenol-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "PG-100", "CG-500" manufactured by Osaka Gas Chemical Co., Ltd.; "YL7760" (bisphenol AF-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL7800" (fluorene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1010" (solid bisphenol A-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1031S" (tetraphenylethane-type epoxy resin) manufactured by Mitsubishi Chemical Corporation, etc.

[0074] 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 of their amounts (liquid epoxy resin: solid epoxy resin) is preferably 1:0.01 to 1:50, more preferably 1:0.05 to 1:20, and further preferably 1:0.1 to 1:10 by mass ratio.

[0075] The epoxy equivalent of the epoxy resin is preferably 50 g / eq. to 5000 g / eq., more preferably 50 g / eq. to 3000 g / eq., further preferably 80 g / eq. to 2000 g / eq., and still further preferably 110 g / eq. to 1000 g / eq. The epoxy equivalent is the mass of the epoxy resin containing 1 equivalent of epoxy groups. This epoxy equivalent can be measured in accordance with JIS K7236.

[0076] The weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and further preferably 400 to 1500. The Mw of the epoxy resin can be measured by gel permeation chromatography (GPC) in the form of values converted to polystyrene.

[0077] When the total of the component (A) and the component (B) in the resin composition is 100% by mass, the content of the component (A) in the resin composition is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 25% by mass or more, 30% by mass or more, and preferably 60% by mass or less, more preferably 50% by mass or less, further preferably 45% by mass or less, or 40% by mass or less.

[0078] In the case where the resin composition contains components other than the component (A) and the component (B), when the non-volatile components in the resin composition are 100% by mass, the content of the component (A) in the resin composition is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, or 6% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, 20% by mass or less, or 10% by mass or less.

[0079] In the case where the resin composition contains components other than the component (A) and the component (B), when the resin components in the resin composition are 100% by mass, the content of the component (A) in the resin composition is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 25% by mass or more, and preferably 60% by mass or less, more preferably 50% by mass or less, further preferably 40% by mass or less, or 35% by mass.

[0080] <(B) Active ester resin>

[0081] The resin composition of the present invention contains an active ester resin as the component (B).

[0082] The active ester moiety contained as the component (B) is preferably an aromatic ester skeleton. The aromatic ester skeleton refers to a skeleton having an ester bond and aromatic rings bonded to one or both ends of the ester bond. Among them, the aromatic ester skeleton preferably has aromatic rings at both ends of the ester bond. As the group having such a skeleton, for example, arylcarbonyloxy, aryloxycarbonyl, arylenedicarbonyl, arylenedioxycarbonyl, arylcarbonylarylene, aryloxycarbonylarylene, arylenedicarbonylarylene, arylenedioxycarbonylarylene, etc. can be mentioned. In addition, the number of carbon atoms of the group having such a skeleton is preferably 7 to 20, more preferably 7 to 15, and further preferably 7 to 11. The aromatic groups such as aryl and arylene may have substituents.

[0083] As the aryl, an aryl having 6 to 30 carbon atoms is preferred, an aryl having 6 to 20 carbon atoms is more preferred, and an aryl having 6 to 10 carbon atoms is further preferred. As such an aryl, for example, a group obtained by removing one hydrogen atom from a monocyclic aromatic compound such as phenyl, furyl, pyrrolyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, etc.; a group obtained by removing one hydrogen atom from a polycyclic aromatic compound such as naphthyl, anthracenyl, phenalenyl, phenanthryl, quinolinyl, isoquinolinyl, quinazolinyl, phthalazinyl, pteridinyl, coumarinyl, indolyl, benzimidazolyl, benzofuranyl, acridinyl, etc. can be mentioned.

[0084] As the arylene, an arylene having 6 to 30 carbon atoms is preferred, an arylene having 6 to 20 carbon atoms is more preferred, and an arylene having 6 to 10 carbon atoms is further preferred. As such an arylene, for example, phenylene, naphthylene, anthrylene, biphenylene (-C 6 H 4 -C 6 H 4 -), etc. can be mentioned.

[0085] The aromatic ester skeleton may have substituents. The substituents are not particularly limited, and for example, a halogen atom, -OH, -O-C 1-6 alkyl, -N(C 1-10 alkyl) 2 , an alkyl having 1 to 20 carbon atoms, an alkenyl having 2 to 30 carbon atoms, an alkynyl having 2 to 30 carbon atoms, an aryl having 6 to 10 carbon atoms, -NH 2 , -CN, -C(O)O-C 1-10 alkyl, -COOH, -C(O)H, -NO 2 , etc. can be mentioned. Here, the term "C p-q " (p and q are positive integers and satisfy p < q) means that the number of carbon atoms of the organic group described immediately after this term is p to q. For example, "C1-10 The expression "alkyl" means an alkyl group having 1 to 10 carbon atoms. These substituents may be bonded to each other to form a ring, and the ring structure also includes a spiro ring and a fused ring.

[0086] <(B1) Active ester resin containing a structural unit represented by formula (B1-1)>

[0087] In the resin composition of the present invention, the (B) active ester resin contains, as the (B1) component, a (B1) active ester resin containing a structural unit represented by the following formula (B1-1) (hereinafter, sometimes referred to as "(B1) active ester resin containing a specific structural unit"). The active ester resin containing a specific structural unit as the (B1) component may be used alone or in combination of two or more.

[0088] [Chemical formula 2]

[0089]

[0090] In formula (B1-1),

[0091] Ar 1 Each independently represents a divalent aromatic group which may have a substituent;

[0092] At least one or more Ar 1 Is a naphthylene group which may have a substituent;

[0093] L B Each independently represents a single bond or a divalent linking group;

[0094] R B1 Represents a divalent hydrocarbon group which may have a substituent, an oxygen atom, a sulfur atom or a divalent group composed of a combination thereof;

[0095] m1 is an integer of 0 to 5;

[0096] "*" represents a bonding bond.

[0097] As the (B1) component, a compound containing an active ester moiety reactive with the (A) component and a structural unit represented by formula (B1-1) can be used. It should be noted that the (B1) component may have a structural unit represented by formula (B1-1) as an active ester moiety. Among them, as the active ester moiety contained in the (B1) component, an aromatic ester skeleton is preferred.

[0098] In formula (B1-1), Ar 1 Each independently represents a divalent aromatic group which may have a substituent. In addition, at least one or more Ar 1 Is a naphthylene group which may have a substituent. From the viewpoint of further enjoying the effects of the present invention, Ar other than the naphthylene group which may have a substituent1 Preferably an arylene group which may have substituents (wherein, naphthylene groups which may have substituents are excluded), more preferably a phenylene group which may have substituents.

[0099] In formula (B1-1), Ar 1 When there are a plurality of them (i.e., when m is an integer of 1 to 5), as long as at least one or more of the Ar 1 is a naphthylene group which may have substituents, the number of naphthylene groups which may have substituents is not particularly limited. In formula (B1-1), Ar 1 When there are a plurality of them, a part of the plurality of Ar 1 may be a naphthylene group which may have substituents, and all of the Ar 1 may be a naphthylene group which may have substituents.

[0100] As the substituents which Ar 1 may have, they are the same as the substituents which the aromatic ester skeleton may have. Among them, as the substituents, more preferably one or more selected from a fluorine atom, -OH, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms.

[0101] In formula (B1-1), L B represents a single bond or a divalent linking group. As the divalent linking group represented by L B shown, there may be mentioned a divalent organic group containing one or more (for example, 1 to 3000, 1 to 1000, 1 to 100, 1 to 50) of skeleton atoms selected from a carbon atom, an oxygen atom, a nitrogen atom, and a sulfur atom. Among them, L B is preferably a single bond, a divalent aromatic group which may have substituents, or a divalent aliphatic group which may have substituents. The divalent aromatic group and the divalent aliphatic group are as described above.

[0102] From the viewpoint of further enjoying the effects of the present invention, the divalent aromatic group represented by L B is preferably an arylene group. The number of carbon atoms of the arylene group in L B is preferably 6 to 24, more preferably 6 to 18, and further preferably 6 to 14. As the arylene group, there may be mentioned, for example, a phenylene group, a naphthylene group, an anthrylene group, a fluorenediyl group (for example, 9H-fluorene-9,9-diyl), a phenanthrenediyl group, an indanediy group, a pyrenediyl group, etc.

[0103] From the viewpoint of further enjoying the effects of the present invention, the divalent aliphatic group represented by L B is preferably a divalent aliphatic group containing one or more of an alkylene group, a cycloalkylene group, an alkenylene group, and a cycloalkenylene group, more preferably a divalent aliphatic group containing one or more of an alkylene group and a cycloalkylene group, and further preferably a cycloalkylene group. L BThe alkylene therein may be either linear or branched, and preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and further preferably 1 to 4 carbon atoms. Examples of the alkylene include methylene, ethylene, propylene, butylene, pentylene, hexylene, etc. L B The cycloalkylene therein preferably has 3 to 15 carbon atoms, more preferably 3 to 12 carbon atoms, and further preferably 3 to 10 carbon atoms. Examples of the cycloalkylene include cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, decahydronaphthylene, norbornylene, dicyclopentylene, adamantylene, etc. L B The alkenylene therein may be either linear or branched, and preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and further preferably 2 to 4 carbon atoms. Examples of the alkenylene include vinylidene, propenylene, butenylene, pentenylene, hexenylene, etc. L B The cycloalkenylene therein preferably has 3 to 15 carbon atoms, more preferably 3 to 12 carbon atoms, and further preferably 3 to 10 carbon atoms. Examples of the cycloalkenylene include cyclopropenylene, cyclobutenylene, cyclopentenylene, cyclohexenylene, norbornenylene, etc.

[0104] As for L B The substituents that it may have are the same as those that the aromatic ester skeleton may have. Among them, as the substituent, it is more preferably one or more selected from a fluorine atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms.

[0105] In formula (B1-1), R B1 represents a divalent hydrocarbon group which may have a substituent, an oxygen atom, a sulfur atom, or a divalent group composed of a combination thereof. Among them, R B1 is preferably a divalent aromatic group, a divalent aliphatic group, or a divalent group composed of a combination thereof. The divalent aromatic group and the divalent aliphatic group are as described above.

[0106] From the viewpoint of further enjoying the effects of the present invention, the divalent aromatic group represented by R B1 is preferably an arylene which may have a substituent. The arylene in R B preferably has 6 to 18 carbon atoms, more preferably 6 to 14 carbon atoms, and further preferably 6 to 10 carbon atoms. This number of carbon atoms does not include the carbon atoms of the substituent. In a preferred embodiment, the divalent aromatic group represented by R B is a phenylene which may have a substituent or a naphthylene which may have a substituent, and more preferably a phenylene which may have a substituent.

[0107] From the viewpoint of further enjoying the effects of the present invention, R B1The divalent aliphatic group shown is preferably an alkylene group which may have a substituent, more preferably an alkenylene group which may have a substituent. R B1 The alkylene group in B1 may be either linear or branched, and preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms. This number of carbon atoms does not include the carbon atoms of the substituent. Examples of such alkylene groups include methylene, ethylene, propylene, butylene, pentylene, hexylene, etc. R B1 The alkenylene group in B1 may be either linear or branched, and preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms. This number of carbon atoms does not include the carbon atoms of the substituent. Examples of alkenylene groups include vinylidene, propenylene, butenylene, pentenylene, hexenylene, etc.

[0108] R B1 The substituent that R may have is the same as the substituent that the aromatic ester skeleton may have. Among them, as this substituent, it is preferably one or more selected from halogen atoms, alkyl groups, alkenyl groups, and aryl groups, more preferably one or more selected from fluorine atoms, alkyl groups having 1 to 6 carbon atoms, alkenyl groups having 2 to 6 carbon atoms, and aryl groups having 6 to 10 carbon atoms.

[0109] In formula (B1-1), m is an integer from 0 to 5, preferably from 0 to 3, and more preferably an integer from 0 to 2.

[0110] The terminal of component (B1) is preferably a monovalent aromatic group. Examples of the monovalent aromatic group include aryl groups as described above. As the monovalent aromatic group possessed by the terminal of component (B1), a phenyl group is preferred.

[0111] The terminal of component (B1) is more preferably an aromatic oxycarbonyl group. As the aromatic oxycarbonyl group at the terminal, a structure represented by aromatic carbon - O - C(=O)- is further preferred, and a structure represented by the following formula (B1-2) is still more preferred.

[0112] [Chemical formula 3]

[0113]

[0114] In formula (B1-2),

[0115] Ar 2 represents a monovalent aromatic group which may have a substituent;

[0116] “*” represents a bonding bond.

[0117] In formula (B1-2), Ar 2 represents a monovalent aromatic group which may have a substituent. The monovalent aromatic group is as described above. From the viewpoint of further enjoying the effects of the present invention, Ar2 Preferably an aryl which may have substituents. Ar 2 The number of carbon atoms of the aryl in is preferably 6 to 18, more preferably 6 to 14, and still more preferably 6 to 10. It should be noted that the number of carbon atoms does not include the carbon atoms of the substituents. In a preferred embodiment, Ar 2 The monovalent aromatic group represented by is a phenyl which may have substituents or a naphthyl which may have substituents.

[0118] Ar 2 The substituents that Ar may have are the same as those that the aromatic ester skeleton may have. Among them, as the substituents, preferably one or more selected from a halogen atom, an alkyl group, an alkenyl group, and an aryl group, and more preferably one or more selected from a fluorine atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms.

[0119] The component (B1) preferably contains a compound represented by the following formula (B1-3).

[0120] [Chemical formula 4]

[0121]

[0122] (In the formula (B1-3), Ar 1 , Ar 2 , L B , R B1 and m1 are the same as above; m2 is an integer of 1 to 10.)

[0123] In the formula (B1-3), Ar 1 , Ar 2 , L B , R B1 and m1 include their preferred examples and ranges as described for the above formulas (B1-1) and (B1-2).

[0124] (B1) The active ester-based resin containing a specific structural unit can be a commercially available product. As the commercially available product, there can be mentioned "EXB-8100L-65T", "EXB-8150-60T", "EXB-8150-62T", "HPC-8150-62T" (manufactured by DIC Corporation), "PC1300-02-65MA" (manufactured by AIR WATER Corporation), etc.

[0125] When the total of the component (B) in the resin composition is 100% by mass, the content of the component (B1) in the resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 13% by mass or more or 14% by mass or more, and preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 85% by mass or less, 83% by mass or less, or 81% by mass or less.

[0126] When the total of the component (A) and the component (B) in the resin composition is 100% by mass, the content of the component (B1) in the resin composition is preferably 5% by mass or more, more preferably 7% by mass or more, still more preferably 9% by mass or more, and preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 55% by mass or less, 53% by mass or less, or 51% by mass or less.

[0127] When the resin composition contains components other than the component (A) and the component (B), when the non-volatile components in the resin composition are 100% by mass, the content of the component (B1) in the resin composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 1.5% by mass or more or 2% by mass or more, and preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 13% by mass or less, 12% by mass or less, or 11% by mass or less.

[0128] When the resin composition contains components other than the component (A) and the component (B), when the resin components in the resin composition are 100% by mass, the content of the component (B1) in the resin composition is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more or 7% by mass or more, and preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 45% by mass or less, 43% by mass or less, or 42% by mass or less.

[0129] <(B2) Allyl-containing active ester resin>

[0130] In the resin composition of the present invention, the (B) active ester resin contains a (B2) allyl-containing active ester resin (hereinafter, sometimes referred to as “(B2) allyl-containing active ester resin”) as the (B2) component. The allyl-containing active ester resin as the (B2) component may be used alone or in combination of two or more. In the present specification, the active ester resin containing the structural unit represented by the formula (B1-1) and allyl is classified as the (B2) component.

[0131] As the (B2) component, a compound containing an active ester moiety reactive with the (A) component and allyl can be used. Among them, the active ester moiety contained in the (B2) component is preferably an aromatic ester skeleton.

[0132] (B2) component preferably has a monovalent aromatic group at its terminal. Examples of the monovalent aromatic group include aryl groups as described above. As the monovalent aromatic group possessed by the terminal of the (B2) component, a phenyl group is preferred.

[0133] In addition to the allyl group and the aromatic ester skeleton, the (B2) component may have any one of an aromatic group, an aliphatic group, and a group composed of a combination thereof.

[0134] As the aromatic group that the (B2) component may have, a divalent aromatic group is preferred, a phenylene group or an arylalkylene group is more preferred, and a phenylene group is further preferred. As the phenylene group, a phenylene group having 6 to 30 carbon atoms is preferred, a phenylene group having 6 to 20 carbon atoms is more preferred, and a phenylene group having 6 to 10 carbon atoms is further preferred. Examples of such a phenylene group include, for example, a phenylene group, a naphthylene group, an anthrylene group, a biphenylene group, etc. As the arylalkylene group, an arylalkylene group having 7 to 30 carbon atoms is preferred, an arylalkylene group having 7 to 20 carbon atoms is more preferred, and an arylalkylene group having 7 to 15 carbon atoms is further preferred. Among them, a phenylene group is preferred.

[0135] As the aliphatic group that the (B2) component may have, a divalent aliphatic group is preferred, a divalent saturated aliphatic group is more preferred, and an alkylene group or a cycloalkylene group is further preferred. As the alkylene group, an alkylene group having 1 to 10 carbon atoms is preferred, an alkylene group having 1 to 6 carbon atoms is more preferred, and an alkylene group having 1 to 3 carbon atoms is further preferred. Examples of the alkylene group include, for example, a methylene group, an ethylene group, a propylene group, 1-methylmethylene, 1,1-dimethylmethylene, 1-methylethylene, 1,1-dimethylethylene, 1,2-dimethylethylene, a butylene group, 1-methylpropylene, 2-methylpropylene, a pentylene group, a hexylene group, etc., and 1,1-dimethylmethylene is preferred.

[0136] As the cycloalkylene group, a cycloalkylene group having 3 to 20 carbon atoms is preferred, a cycloalkylene group having 3 to 15 carbon atoms is more preferred, and a cycloalkylene group having 5 to 10 carbon atoms is further preferred. The cycloalkylene group may have a monocyclic structure or a polycyclic structure. Examples of the cycloalkylene group include, for example, a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cyclopentylene group, a cycloheptylene group, and cycloalkylene groups represented by the following formulas (a) to (d). In formulas (a) to (d), "*" represents a bonding bond.

[0137] [Chemical formula 5]

[0138]

[0139] As a group composed of their combination, preferably a divalent group, examples thereof include a group composed of a combination of an aliphatic group and an aromatic group, a group composed of a combination of an aromatic group, an aliphatic group, and an aromatic group, etc. As an embodiment of the group composed of these combinations, it is a group composed of a combination of arylene-alkylene-arylene, preferably a group composed of a combination of phenylene-1,1-dimethylmethylene-phenylene.

[0140] (Component (B2) contains allyl. From the viewpoint of significantly obtaining the desired effects of the present invention, the number of allyl groups per molecule of component (B2) is preferably 1 or more, more preferably 2 or more, preferably 10 or less, more preferably 8 or less, and further preferably 5 or less.

[0141] The allyl group contained in component (B2) may be present as a substituent of a terminal monovalent aromatic group, or may be present as a substituent of an aromatic group or an aliphatic group. When component (B2) contains an allyl group as a substituent of a terminal monovalent aromatic group, component (B2) preferably contains an allyl group as a substituent of the aromatic groups at both ends.

[0142] (The aromatic group and aliphatic group that component (B2) can have may further have substituents. The substituents are not particularly limited, and examples thereof include a halogen atom, -OH, -O-C 1-6 alkyl, -N(C 1-10 alkyl) 2 , an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, an aryl group having 6 to 10 carbon atoms, -NH 2 , -CN, -C(O)O-C 1-10 alkyl, -COOH, -C(O)H, -NO 2 , etc.

[0143] (Component (B2) is preferably any one of the compounds represented by the following formula (B2-1) and the compounds represented by the following formula (B2-2).

[0144] [Chemical formula 6]

[0145]

[0146] In formula (B2-1),

[0147] Ar 11 each independently represents a monovalent aromatic group that may have a substituent;

[0148] Ar 12 each independently represents a divalent aromatic group that may have a substituent;

[0149] R B2 each independently represents a divalent hydrocarbon group which may have a substituent, an oxygen atom, a sulfur atom, or a divalent group composed of a combination thereof;

[0150] Ar 11 、Ar 12 and R B2 at least one of them has an allyl group as a substituent;

[0151] n a represents an integer from 0 to 10.

[0152] [Chemical Formula 7]

[0153]

[0154] In formula (B2-2),

[0155] Ar 21 each independently represents a monovalent aromatic group which may have a substituent;

[0156] Ar 22 each independently represents a divalent aromatic group which may have a substituent;

[0157] R B3 each independently represents a divalent hydrocarbon group which may have a substituent, an oxygen atom, a sulfur atom, or a divalent group composed of a combination thereof;

[0158] Ar 21 、Ar 22 and R B3 at least one of them has an allyl group as a substituent;

[0159] n b represents an integer from 0 to 10.

[0160] In formula (B2-1), Ar 11 each independently represents a monovalent aromatic group which may have a substituent. Examples of the monovalent aromatic group include groups obtained by removing one hydrogen atom from a monocyclic aromatic compound such as a phenyl group, a furyl group, a pyrrolyl group, a thienyl group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group, an isothiazolyl group, a pyridyl group, a pyrimidinyl group, a pyridazinyl group, a pyrazinyl group, a triazinyl group; groups obtained by removing one hydrogen atom from a polycyclic aromatic compound such as a naphthyl group, an anthryl group, a phenalenyl group, a phenanthryl group, a quinolinyl group, an isoquinolinyl group, a quinazolinyl group, a phthalazinyl group, a pteridinyl group, a coumarinyl group, an indolyl group, a benzimidazolyl group, a benzofuryl group, an acridinyl group, etc. In addition, Ar 11 in formula (B2-1) may be different from each other, but are preferably the same. Among them, from the viewpoint of significantly obtaining the effects of the present invention, Ar 11 is preferably a phenyl group.

[0161] As Ar 11 The substituents that can be possessed are the same as those that the aromatic ester skeleton can possess.

[0162] In formula (B2-1), Ar 12 Each independently represents a divalent aromatic group that may have substituents. The divalent aromatic group is as described above.

[0163] As Ar 12 The substituents that can be possessed are the same as those that the aromatic ester skeleton can possess.

[0164] In formula (B2-1), R B2 Each independently represents a divalent hydrocarbon group that may have substituents, an oxygen atom, a sulfur atom, or a divalent group composed of a combination thereof. As the divalent hydrocarbon group, a divalent aromatic group, a divalent aliphatic group, or a divalent group composed of a combination thereof can be cited.

[0165] In formula (B2-1), R B2 Is preferably a divalent group formed by combining a divalent aromatic group that may have substituents, a divalent aliphatic group that may have substituents, and an oxygen atom, and more preferably a divalent group formed by alternately combining a plurality of divalent aromatic groups that may have substituents and a plurality of divalent aliphatic groups that may have substituents. The divalent aromatic group and the divalent aliphatic group are as described above. As specific examples of these combined divalent groups, the divalent groups shown in the following formulas (B2-1-1) to (B2-1-9) can be cited. In the formulas, b1 to b7 represent integers from 0 to 10, preferably integers from 0 to 5. "*" represents a bonding bond, and the wavy line represents a structure obtained by reacting an aromatic compound, an acyl halide of an aromatic compound, or an esterified product of an aromatic compound used in the synthesis of the (B2) component.

[0166] [Chemical formula 8]

[0167]

[0168] [Chemical formula 9]

[0169]

[0170] As R B2 The substituents that can be possessed are the same as those that the aromatic ester skeleton can possess.

[0171] In formula (B2-1), Ar 11 , Ar 12 and R B2 At least one of them has an allyl group as a substituent. Among them, Ar 11At least one of them preferably has an allyl group as a substituent. Further, more preferably, all of the Ar 11 has an allyl group as a substituent.

[0172] In formula (B2-1), n a represents an integer from 0 to 10. Among them, n a is preferably an integer from 0 to 5, and more preferably an integer from 0 to 3. It should be noted that when the compound represented by formula (B2-1) is an oligomer or a polymer, n a represents the average value thereof.

[0173] The compound represented by formula (B2-1) is preferably the compound represented by the following formula (B2-3).

[0174] [Chemical formula 10]

[0175]

[0176] In formula (B2-3),

[0177] Ar 31 each independently represents a monovalent aromatic group having an allyl group as a substituent;

[0178] Ar 32 each independently represents a divalent aromatic group which may have a substituent;

[0179] R B4 each independently represents a divalent group formed by combining a divalent aromatic group which may have a substituent, a divalent aliphatic group which may have a substituent, and an oxygen atom;

[0180] n a1 represents an integer from 0 to 10.

[0181] In formula (B2-3), Ar 31 each independently represents a monovalent aromatic group having an allyl group as a substituent. The monovalent aromatic group is as described above. Among them, from the viewpoint of significantly obtaining the effects of the present invention, Ar 31 is preferably a phenyl group having an allyl group as a substituent.

[0182] Ar 31 may have a substituent other than an allyl group. As this substituent, it is the same as the substituent that the aromatic ester skeleton may have.

[0183] In formula (B2-3), Ar 32 each independently represents a divalent aromatic group which may have a substituent, which is the same as Ar 12 in formula (B2-1).

[0184] In formula (B2-3), RB4 Each independently represents a divalent group formed by combining a divalent aromatic group which may have a substituent, a divalent aliphatic group which may have a substituent, and an oxygen atom. Among them, R B4 is preferably a divalent group formed by alternately combining a plurality of divalent aromatic groups which may have a substituent and a plurality of divalent aliphatic groups which may have a substituent. As R B4 specific examples, the divalent groups represented by the above formulas (B2-1-1) to (B2-1-6) can be cited.

[0185] As R B4 The substituents that can be had are the same as those that the aromatic ester skeleton can have.

[0186] In formula (B2-3), n a1 represents an integer from 0 to 10, which is the same as n a in formula (B2-1).

[0187] In formula (B2-2), Ar 21 each independently represents a monovalent aromatic group which may have a substituent. The monovalent aromatic group is as described above. Ar in formula (B2-2) 21 can be different from each other, but are preferably the same. Among them, from the viewpoint of significantly obtaining the effects of the present invention, Ar 21 is preferably a phenyl group.

[0188] As the substituents that Ar 21 can have, they are the same as those that the aromatic ester skeleton can have.

[0189] In formula (B2-2), Ar 22 each independently represents a divalent aromatic group which may have a substituent. The divalent aromatic group is as described above.

[0190] As the substituents that Ar 22 can have, they are the same as those that the aromatic ester skeleton can have.

[0191] In formula (B2-2), R B3 each independently represents a divalent hydrocarbon group which may have a substituent, an oxygen atom, a sulfur atom, or a divalent group composed of a combination thereof. The divalent hydrocarbon group is as described above. Among them, R B3Preferably, it is a divalent group formed by combining a divalent aromatic group which may have substituents and a divalent aliphatic group which may have substituents. More preferably, it is a divalent group formed by combining in the order of a divalent aromatic group which may have substituents - a divalent aliphatic group which may have substituents - a divalent aromatic group which may have substituents. Further preferably, it is a divalent group having in the order of phenylene-1,1-dimethylmethylene-phenylene. The divalent group having in the order of phenylene-1,1-dimethylmethylene-phenylene refers to the group obtained by removing the allyl group from the above formula (B2-1-9), specifically shown by the following formula (B2-1-10). In the formula, "*" represents a bonding bond.

[0192] [Chemical formula 11]

[0193]

[0194] As R B3 The substituents that can be had are the same as those that the aromatic ester skeleton can have.

[0195] In formula (B2-2), Ar 21 , Ar 22 and R B3 At least one of them has an allyl group as a substituent. Among them, it is preferred that at least one of R B3 has an allyl group as a substituent. Further, more preferably, R B3 has an allyl group as a substituent of the divalent aromatic group.

[0196] In formula (B2-2), n b represents an integer from 0 to 10, preferably represents an integer from 1 to 5, more preferably represents an integer from 1 to 3, and particularly preferably is 1. It should be noted that when the compound represented by formula (B2-2) is an oligomer or a polymer, n b represents its average value.

[0197] The compound represented by formula (B2-2) is preferably the compound represented by the following formula (B2-4).

[0198] [Chemical formula 12]

[0199]

[0200] In formula (B2-4),

[0201] Ar 41 Each independently represents a monovalent aromatic group which may have substituents;

[0202] Ar 42 Each independently represents a divalent aromatic group having an allyl group as a substituent;

[0203] Ar 43 Each independently represents a divalent aromatic group which may have substituents;

[0204] R B5 Each independently represents a divalent aliphatic hydrocarbon group which may have substituents;

[0205] n b1 Represents an integer from 0 to 10.

[0206] In formula (B2-4), Ar 41 Each independently represents a monovalent aromatic hydrocarbon group which may have substituents, and is the same as Ar in formula (B2-2). Ar in formula (B2-4) 21 May be different from each other, but are preferably the same. 41 As the substituents that Ar

[0207] May have, they are the same as the substituents that the aromatic ester skeleton may have. 41

[0208] In formula (B2-4), Ar 42 Each independently represents a divalent aromatic group having an allyl group as a substituent. The divalent aromatic group is as described above. Among them, from the viewpoint of significantly obtaining the effects of the present invention, Ar 42 Is preferably a phenylene group having an allyl group as a substituent.

[0209] Ar 42 May have substituents other than the allyl group. As such substituents, they are the same as the substituents that the aromatic ester skeleton may have.

[0210] In formula (B2-4), Ar 43 Each independently represents a divalent aromatic group which may have substituents. The divalent aromatic group is as described above. Among them, from the viewpoint of significantly obtaining the effects of the present invention, Ar 43 Is preferably a phenylene group which may have substituents.

[0211] In formula (B2-4), R B5 Each independently represents a divalent aliphatic hydrocarbon group which may have substituents. Among them, from the viewpoint of significantly obtaining the effects of the present invention, R B5 Is preferably 1,1-dimethylmethylene.

[0212] In formula (B2-4), n b1 Represents an integer from 0 to 10, and is the same as n in formula (B2-2). b

[0213] ​As specific examples of the component (B2), compounds represented by the following formula (B2-5), the following formula (B2-6), or the following formula (B2-7) can be cited. In addition, as specific examples of the component (B2), compounds described in paragraphs 0068 to 0071 of International Publication No. 2018 / 235424 and paragraphs 0113 to 0115 of International Publication No. 2018 / 235425 can be cited. Among them, the component (B2) is not limited to these specific examples. In formula (B2-5), s represents an integer of 0 or more, and r represents an integer of 1 to 10. In formula (B2-6), the average value of n b2 is 1. In formula (B2-7), n and m each independently represent an integer of 0 or more.

[0214] [Chemical formula 13]

[0215]

[0216]

[0217] As the component (B2), products synthesized by known methods can be used. The synthesis of the component (B2) can be carried out by, for example, the methods described in International Publication No. 2018 / 235424 or International Publication No. 2018 / 235425.

[0218] From the viewpoint of significantly obtaining the effects of the present invention, the weight-average molecular weight of the component (B2) is preferably 150 or more, more preferably 200 or more, still more preferably 250 or more, and preferably 5000 or less, more preferably 3000 or less, still more preferably 2000 or less. The weight-average molecular weight of the component (B2) is the weight-average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

[0219] From the viewpoint of significantly obtaining the effects of the present invention, the allyl equivalent of the component (B2) is preferably 50 g / eq. or more, more preferably 100 g / eq. or more, still more preferably 150 g / eq., and preferably 2000 g / eq. or less, more preferably 1000 g / eq. or less, still more preferably 500 g / eq. or less. The allyl equivalent is the mass of the component (B2) containing 1 equivalent of allyl.

[0220] When the total of the component (B) in the resin composition is set to 100% by mass, the content of the component (B2) in the resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, 17% by mass or more, or 19% by mass or more, and preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 88% by mass or less, or 86% by mass or less.

[0221] When the total of component (A) and component (B) in the resin composition is 100% by mass, the content of component (B2) in the resin composition is preferably 5% by mass or more, more preferably 8% by mass or more, still more preferably 10% by mass or more or 11% by mass or more, and preferably 70% by mass or less, more preferably 65% by mass or less, still more preferably 60% by mass or less or 59% by mass or less.

[0222] The mass ratio of the content of component (B2) to the content of component (B1) in the resin composition ((B2) component / (B1) component) is preferably 0.1 or more, more preferably 0.15 or more, still more preferably 0.2 or more, 0.23 or more or 0.24 or more, and preferably 10 or less, more preferably 8 or less, still more preferably 6 or less.

[0223] When the resin composition contains components other than component (A) and component (B), when the non-volatile components in the resin composition are 100% by mass, the content of component (B2) in the resin composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 1.5% by mass or more, 2% by mass or more or 2.5% by mass or more, and preferably 25% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less or 14% by mass or less.

[0224] When the resin composition contains components other than component (A) and component (B), when the resin components in the resin composition are 100% by mass, the content of component (B2) in the resin composition is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 7% by mass or more, 9% by mass or more or 10% by mass or more, and preferably 60% by mass or less, more preferably 55% by mass or less, still more preferably 50% by mass or less.

[0225] <(B3) Other active ester resins>

[0226] In the resin composition of the present invention, in addition to component (B1) and component (B2), component (B) active ester resin may further contain (B3) other active ester resins as optional components. The (B3) other active ester resins as component (B3) do not include those belonging to the above-mentioned component (A), component (B1), and component (B2). The (B3) other active ester resins may be used alone or in combination of two or more.

[0227] As the component (B3), there is no particular limitation. Usually, compounds having two or more highly reactive ester groups in one molecule, such as phenol esters, benzenethiol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, etc., are preferably used. The component (B3) is preferably a substance obtained by the condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester-based curing agent obtained from a carboxylic acid compound and a phenol compound is more preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, etc. Examples of the phenol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, trihydroxybenzene, dicyclopentadiene-type diphenol compound, phenol novolac, etc. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol and one molecule of dicyclopentadiene.

[0228] Specifically, an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing an acetylated product of phenol novolac, and an active ester compound containing a benzoylated product of phenol novolac are preferred, and among them, an active ester compound containing a dicyclopentadiene-type diphenol structure is more preferred. The "dicyclopentadiene-type diphenol structure" represents a divalent structural unit composed of phenylene-dicyclopentene-phenylene.

[0229] Examples of commercially available products of the component (B3) include "EXB-9451", "EXB-9460", "EXB-9460S", "HPC-8000-65T", "HPC-8000L-65TM" (manufactured by DIC Corporation) for the active ester compound containing a dicyclopentadiene-type diphenol structure; "DC808" (manufactured by Mitsubishi Chemical Corporation) for the active ester compound containing an acetylated product of phenol novolac; "YLH1026" (manufactured by Mitsubishi Chemical Corporation) for the active ester compound containing a benzoylated product of phenol novolac; "DC808" (manufactured by Mitsubishi Chemical Corporation) for the active ester-based curing agent containing an acetylated product of phenol novolac; and "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation), etc. for the active ester-based curing agent containing a benzoylated product of phenol novolac.

[0230] When the resin composition of the present invention contains the component (B3), when the total of the component (B) in the resin composition is set to 100% by mass, the content of the component (B3) in the resin composition is, for example, 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, further preferably 1% by mass or more, and for example, 15% by mass or less, preferably 10% by mass or less, more preferably 7% by mass or less, further preferably 5% by mass or less, 4% by mass or less, or 3% by mass or less.

[0231] When the resin composition of the present invention contains the component (B3), when the non-volatile components in the resin composition are set to 100% by mass, the content of the component (B3) in the resin composition is, for example, 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 1% by mass or more, further preferably 2% by mass or more, and for example, 15% by mass or less, preferably 10% by mass or less, more preferably 7% by mass or less, further preferably 5% by mass or less, 4% by mass or less, or 3% by mass or less.

[0232] When the resin composition of the present invention contains the component (B3), when the resin components in the resin composition are set to 100% by mass, the content of the component (B3) in the resin composition is, for example, 0.1% by mass or more, preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 7% by mass or more, 9% by mass or more, or 10% by mass or more, and for example, 25% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 13% by mass or less, 12% by mass or less, and 11% by mass or less.

[0233] As the quantitative ratio of the component (A) and the component (B), in terms of the ratio of [(total count of epoxy groups of the component (A))]∶[(total count of active ester groups of the component (B))], it is preferably in the range of 1∶0.01 to 1∶10, more preferably in the range of 1∶0.1 to 1∶5, further preferably in the range of 1∶0.2 to 1∶3, further more preferably in the range of 1∶0.3 to 1∶2, still further preferably in the range of 1∶0.8 to 1∶2, still more preferably in the range of 1∶1 to 1∶1.8, particularly preferably in the range of 1∶1.2 to 1∶1.6, and more particularly preferably in the range of 1∶1.3 to 1∶1.5. Here, the "total count of epoxy groups of the component (A)" refers to the value obtained by summing up all the values obtained by dividing the mass of the component (A) present in the resin composition by the epoxy equivalent. In addition, the "total count of active ester groups of the component (B)" refers to the value obtained by summing up all the values obtained by dividing the mass of the component (B) present in the resin composition by the active ester group equivalent. As the component (B), by making the quantitative ratio with the component (A) within the above range, the effects of the present invention can be significantly obtained.

[0234] When the total of component (A) and component (B) in the resin composition is 100% by mass, the content of component (B) in the resin composition is preferably 30% by mass or more, more preferably 40% by mass or more, still more preferably 50% by mass or more, 55% by mass or more, or 60% by mass or more, and preferably 80% by mass or less, more preferably 75% by mass or less, still more preferably 70% by mass or less.

[0235] When the resin composition contains components other than component (A) and component (B), when the non-volatile components in the resin composition are 100% by mass, the content of component (B) in the resin composition is preferably 5% by mass or more, more preferably 8% by mass or more, still more preferably 10% by mass or more, 12% by mass or more, or 13% by mass or more, and preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less, 18% by mass or less, or 16% by mass.

[0236] When the resin composition contains components other than component (A) and component (B), when the resin components in the resin composition are 100% by mass, the content of component (B) in the resin composition is preferably 30% by mass or more, more preferably 40% by mass or more, still more preferably 45% by mass or more, 48% by mass or more, or 50% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less, or 59% by mass or less.

[0237] <(C) Inorganic filler>

[0238] The resin composition of the present invention may further contain an inorganic filler as component (C). By containing component (C), there is a tendency to further reduce the thermal expansion rate and the dielectric loss tangent.

[0239] Examples of the material as component (C) include, for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, 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, and zirconium tungstate phosphate, etc. Among them, silica is particularly suitable. Examples of silica include, for example, amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, etc. In addition, as silica, spherical silica is preferred. Component (C) can be used alone or in combination of two or more.

[0240] Examples of commercially available products as the component (C) include, for example, "SP60-05" and "SP507-05" manufactured by Nippon Steel Chemical & Materials Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", "YA010C", "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1" manufactured by Admatechs Co., Ltd.; "UFP-30", "DAW-03", and "FB-105FD" manufactured by Denka Co., Ltd.; "SilfilNSS-3N", "SilfilNSS-4N", and "SilfilNSS-5N" manufactured by Tokuyama Corporation; "CELLSPHERES" and "MGH-005" manufactured by Taiheiyo Cement Corporation, etc.

[0241] The average particle diameter of the component (C) is not particularly limited, preferably 10 μm or less, more preferably 5 μm or less, 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, preferably 0.01 μm or more, more preferably 0.05 μm or more, still more preferably 0.07 μm or more, 0.1 μm or more, or 0.2 μm or more. The average particle diameter of the component (C) can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, a particle size distribution of the inorganic filler can be created based on volume using a laser diffraction / scattering particle size distribution measuring device, and the median diameter thereof can be set as the average particle diameter for measurement. As the measurement sample, a sample obtained by weighing 100 mg of the inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing them ultrasonically for 10 minutes can be used. For the measurement sample, a laser diffraction type particle size distribution measuring device is used, the light source wavelength used is set to blue and red, the particle size distribution of the inorganic filler based on volume is measured in a flow cell manner, and the average particle diameter as the median diameter is calculated from the obtained particle size distribution. Examples of the laser diffraction type particle size distribution measuring device include "LA-960" manufactured by Horiba, Ltd.

[0242] (C) The specific surface area of the component is not particularly limited, 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, 3 m 2 / g or more, or 5 m 2 / g or more. The upper limit of the specific surface area is not particularly limited, 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 2Less than / g. The specific surface area of the (C) component can be obtained by adsorbing nitrogen on the surface of the sample using a specific surface area measuring device ("Macsorb HM-1210" manufactured by Mountech Co., Ltd.) according to the BET method and calculating the specific surface area using the BET multi-point method.

[0243] (C) component is preferably surface-treated with a suitable surface treatment agent. By performing surface treatment, the moisture resistance and dispersibility of the (C) component can be improved. Examples of the surface treatment agent include, for example, vinyl silane coupling agents, epoxy silane coupling agents, styryl silane coupling agents, (meth)acrylic silane coupling agents, amino silane coupling agents, isocyanurate silane coupling agents, ureido silane coupling agents, mercapto silane coupling agents, isocyanate silane coupling agents, acid anhydride silane coupling agents, etc. silane coupling agents; non-silane coupling - alkoxysilane compounds such as methyltrimethoxysilane and phenyltrimethoxysilane; silazane compounds, etc. The surface treatment agent can be used alone or in combination of two or more.

[0244] Examples of commercially available products of the surface treatment agent include, for example, "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., etc.

[0245] From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment with the surface treatment agent is preferably controlled within a specified range. Specifically, 100% by mass of the inorganic filler is preferably surface-treated with 0.2 to 5% by mass of the surface treatment agent.

[0246] The degree of surface treatment with the surface treatment agent can be evaluated by the carbon amount per unit surface area of the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the carbon amount per unit surface area of the inorganic filler is preferably 0.02 mg / m 2 Above, more preferably 0.1 mg / m 2 Above, further preferably 0.2 mg / m 2 Above. On the other hand, from the viewpoint of preventing the increase in the melt viscosity of the resin composition and the melt viscosity in the sheet form, the carbon amount per unit surface area of the inorganic filler is preferably 1 mg / m 2 Below, more preferably 0.8 mg / m 2 Below, further preferably 0.5 mg / m 2As follows. The carbon amount per unit surface area of the component (C) can be measured after washing the surface-treated inorganic filler with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with a surface treatment agent, and ultrasonic washing is performed at 25°C for 5 minutes. After removing the supernatant and drying the solid component, a carbon analyzer can be used to measure the carbon amount per unit surface area of the inorganic filler. As the carbon analyzer, “EMIA-320V” manufactured by Horiba, Ltd. etc. can be used.

[0247] When the resin composition of the present invention contains the component (C), from the viewpoint of easily achieving a resin composition with a lower dielectric loss tangent and coefficient of thermal expansion, when the non-volatile components in the resin composition are set to 100% by mass, the content of the component (C) in the resin composition is, for example, 40% by mass or more, preferably 50% by mass or more, more preferably 60% by mass or more, 65% by mass or more, or 70% by mass or more. The upper limit of the content of the component (C) is not particularly limited, and can be set to, for example, 90% by mass or less, 85% by mass or less, 80% by mass or less, 77% by mass or less, or 75% by mass or less, etc. Even when the resin composition of the present invention contains the component (C) at a high content in order to further reduce the dielectric loss tangent and coefficient of thermal expansion of the cured product of the resin composition, a cured product with excellent stain removability and excellent adhesion strength to the conductor layer can be obtained.

[0248] <(D) Other thermosetting resins>

[0249] The resin composition of the present invention may further contain a thermosetting resin (sometimes referred to as “other thermosetting resin”) other than the components (A) and (B) as the component (D).

[0250] Examples of the component (D) include, for example, phenol resins, naphthol resins, acid anhydride resins, cyanate ester resins, carbodiimide resins, amine resins, etc. The component (D) can be used alone or in combination of two or more.

[0251] As the phenol resins and naphthol resins, those having a novolac structure are preferred from the viewpoints of heat resistance and water resistance. In addition, from the viewpoint of adhesion to the conductor layer, nitrogen-containing phenol resins and nitrogen-containing naphthol resins are preferred, and phenol resins containing a triazine skeleton and naphthol resins containing a triazine skeleton are more preferred.

[0252] As specific examples of phenol resins and naphthol resins, for example, "MEH-7700", "MEH-7810", "MEH-7851", "MEH-8000H" manufactured by Meiwafosis Co., Ltd.; "NHN", "CBN", "GPH" manufactured by Nippon Kayaku Co., Ltd.; "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-495V", "SN-375", "SN-395" manufactured by Nippon Steel Chemical & Materials Co., Ltd.; "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" manufactured by DIC Corporation; "GDP-6115L", "GDP-6115H", "ELPC75", etc. manufactured by Gunei Chemical Industry Co., Ltd.

[0253] As acid anhydride resins, resins having one or more acid anhydride groups in one molecule can be cited. As specific examples of acid anhydride resins, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfone tetracarboxylic 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(dehydrated trimellitate), polymer-type acid anhydrides such as styrene-maleic acid resin copolymerized from styrene and maleic acid, etc. As commercially available products of acid anhydride resins, "MH-700", etc. manufactured by Shin Nippon Rika Co., Ltd. can be cited.

[0254] Examples of the cyanate ester resin include bifunctional cyanate ester resins such as bisphenol A dicyanate, polyphenol cyanate, oligomeric (3-methylidene-1,5-phenylene cyanate), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanatephenyl) sulfide, and bis(4-cyanatephenyl) ether; polyfunctional cyanate ester resins derived from phenol novolac and cresol novolac; and prepolymers in which a part of these cyanate ester resins is triazinized. Specific examples of the cyanate ester resin include "PT30" and "PT60" (phenol novolac type polyfunctional cyanate ester resins), "ULL-950S" (polyfunctional cyanate ester resin), "BA230", and "BA230S75" (prepolymers in which a part or all of bisphenol A dicyanate is triazinized to form a trimer) manufactured by arxada.

[0255] Specific examples of the carbodiimide resin include CARBODILITE (registered trademark) V-03 (carbodiimide equivalent: 216 g / eq.), V-05 (carbodiimide equivalent: 262 g / eq.), V-07 (carbodiimide equivalent: 200 g / eq.), V-09 (carbodiimide equivalent: 200 g / eq.) manufactured by Nisshinbo Chemical Inc.; and Stabaxol (registered trademark) P (carbodiimide equivalent: 302 g / eq.) manufactured by LANXESS.

[0256] As the amine-based resin, resins having one or more amino groups in one molecule can be cited. For example, aliphatic amines, polyetheramines, alicyclic amines, aromatic amines, etc. can be cited. Specific examples of the amine-based resin include 4,4'-methylenebis(2,6-dimethylaniline), diphenylsulfone diamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, m-phenylenediamine, m-xylenediamine, 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-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, etc. The amine-based resin can be a commercially available product. For example, "KAYABOND C-200S", "KAYABOND C-100", "KAYABOND A-A", "KAYABOND A-B", "KAYABOND A-S" manufactured by Nippon Kayaku Co., Ltd., "Epicure W" manufactured by Mitsubishi Chemical Corporation, etc. can be cited.

[0257] When the resin composition of the present invention contains the component (D), the quantitative ratio of the component (A), the component (B), and the component (D) is preferably in the range of 1:0.01 to 1:10, more preferably in the range of 1:0.05 to 1:8, further preferably in the range of 1:0.1 to 1:5, still further preferably in the range of 1:0.5 to 1:3, still further preferably in the range of 1:1 to 1:2.5, still still further preferably in the range of 1:1.3 to 1:2, and particularly preferably in the range of 1:1.5 to 1:1.8, in terms of the ratio of [(total count of epoxy groups of the component (A))]:[(total count of active groups of the component (B) and the component (D))]. The "total count of epoxy groups of the component (A)" is as described above. In addition, the "total count of active groups of the component (B) and the component (D)" means the value obtained by dividing the mass of the component (B) present in the resin composition by the active ester group equivalent and the value obtained by dividing the mass of the component (D) by the active group equivalent, all added together. When the resin composition of the present invention contains the component (D), as the component (B) and the component (D), by making the quantitative ratio with the component (A) within the above range, the effects of the present invention can be significantly obtained.

[0258] When the resin composition of the present invention contains the component (D), when the non-volatile components in the resin composition are set to 100% by mass, the content of the component (D) in the resin composition is, for example, 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 1% by mass or more, and further preferably 2% by mass or more, and is, for example, 15% by mass or less, preferably 10% by mass or less, more preferably 7% by mass or less, and further preferably 5% by mass or less or 4% by mass or less.

[0259] When the resin composition of the present invention contains the component (D), when the resin components in the resin composition are set to 100% by mass, the content of the component (D) in the resin composition is, for example, 0.1% by mass or more, preferably 1% by mass or more, more preferably 5% by mass or more, and further preferably 7% by mass or more, and is, for example, 25% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 13% by mass or less or 12% by mass or less.

[0260] <(E) Organic filler>

[0261] The resin composition of the present invention may further contain an organic filler as the component (E). The (E) organic filler may be used alone or in combination of two or more.

[0262] As the organic filler, an organic filler containing a rubber component can be widely used. Examples of the rubber component contained in the organic filler include silicone-based elastomers such as polydimethylsiloxane; olefin-based thermoplastic elastomers such as polybutadiene, polyisoprene, polychloroprene, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-isobutene copolymer, acrylonitrile-butadiene copolymer, isoprene-isobutene copolymer, isobutene-butadiene copolymer, ethylene-propylene-diene terpolymer, and ethylene-propylene-butene terpolymer; and thermoplastic elastomers such as acrylic-based thermoplastic elastomers such as poly(propyl) (meth)acrylate, poly(butyl) (meth)acrylate, poly(cyclohexyl) (meth)acrylate, and poly(octyl) (meth)acrylate. Further, a silicone-based rubber such as polyorganosiloxane rubber can be mixed in the rubber component. The glass transition temperature (Tg) of the rubber component contained in the rubber particles is, for example, 0°C or lower, preferably -10°C or lower, more preferably -20°C or lower, and further preferably -30°C or lower.

[0263] In one embodiment, the organic filler material is a core-shell type rubber particle including a core particle and a shell portion. The core particle contains the rubber components listed above, and the shell portion is a shell portion formed by graft copolymerizing a monomer component capable of copolymerizing with the rubber components contained in the core particle. Here, the core-shell type does not necessarily refer only to those in which the core particle and the shell portion can be clearly distinguished, but also includes those in which the boundary between the core particle and the shell portion is unclear, and the core particle may not be completely covered by the shell portion.

[0264] As specific examples of the organic filler material containing a rubber component, for example, "CHT" manufactured by Samsung SDI Co., Ltd.; "B602" manufactured by Techno UMG Co., Ltd.; "PARALOID EXL-2602", "PARALOID EXL-2603", "PARALOID EXL-2655", "PARALOID EXL-2311", "PARALOID-EXL2313", "PARALOIDEXL-2315", "PARALOID KM-330", "PARALOID KM-336P", "PARALOID KCZ-201" manufactured by DOW Co., Ltd.; "METABLEN C-223A", "METABLEN E-901", "METABLEN S-2001", "METABLENW-450A", "METABLEN SRK-200" manufactured by Mitsubishi Rayon Co., Ltd.; "Kane Ace M-511", "Kane Ace M-600", "Kane AceM-400", "Kane Ace M-580", "Kane Ace MR-01" manufactured by KANEKA Co., Ltd.; "STAFYROID AC3355", "STAFYROID AC3816", "STAFYROID AC3832", "STAFYROID AC4030", "STAFYROID AC3364" manufactured by AICA Industries Co., Ltd., etc. These are core-shell type rubber particles.

[0265] When the resin composition of the present invention contains the component (E), when the non-volatile component in the resin composition is set to 100% by mass, the content of the component (E) in the resin composition is, for example, 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, and for example, 15% by mass or less, preferably 10% by mass or less, more preferably 7% by mass or less, further preferably 5% by mass or less, 4% by mass or less, or 3% by mass or less.

[0266] When the resin composition of the present invention contains the component (E), when the resin component in the resin composition is set to 100% by mass, the content of the component (E) in the resin composition is, for example, 0.1% by mass or more, preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 4% by mass or more, and, for example, 20% by mass or less, preferably 15% by mass or less, more preferably 10% by mass or less, further preferably 8% by mass or less.

[0267] <(F) Curing accelerator>

[0268] The resin composition of the present invention may further contain a curing accelerator as the component (F).

[0269] Examples of the component (F) include a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, a guanidine-based curing accelerator, a metal-based curing accelerator, a peroxide-based curing accelerator, and the like. The curing accelerator may be used alone or in combination of two or more.

[0270] When the resin composition of the present invention contains the component (F), when the non-volatile component in the resin composition is set to 100% by mass, the content of the component (F) in the resin composition is, for example, 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 0.2% by mass or more, further preferably 0.25% by mass or more, and, for example, 5% by mass or less, preferably 3% by mass or less, more preferably 2% by mass or less, further preferably 1% by mass or less.

[0271] When the resin composition of the present invention contains the component (F), when the resin component in the resin composition is set to 100% by mass, the content of the component (F) in the resin composition is, for example, 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably 1.1% by mass or more, and, for example, 10% by mass or less, preferably 7% by mass or less, more preferably 5% by mass or less, further preferably 3% by mass or less.

[0272] <(G) Optional additive>

[0273] The resin composition of the present invention may further contain (G) optional additives. Examples of such additives include radical polymerization initiators such as peroxide-based radical polymerization initiators and azo-based radical polymerization initiators; thermoplastic resins such as phenoxy resins, polyvinyl acetal resins, polysulfone resins, polyethersulfone resins, polyetheretherketone resins, and polyester resins; organometallic compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as silicone-based leveling agents and acrylic polymer-based leveling agents; thickeners such as bentonite and montmorillonite; defoaming agents such as silicone-based defoaming agents, acrylic-based defoaming agents, fluorine-based defoaming agents, and vinyl resin-based defoaming agents; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; adhesion improvers such as urea silane; adhesion imparting agents such as triazole-based adhesion imparting agents, tetrazole-based adhesion imparting agents, and triazine-based adhesion imparting agents; antioxidants such as hindered phenol-based antioxidants; fluorescent brighteners such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; flame retardants such as phosphorus-based flame retardants (e.g., phosphate ester compounds, phosphazine compounds, phosphonic acid compounds, red phosphorus), nitrogen-based flame retardants (e.g., melamine sulfate), halogen-based flame retardants, and inorganic flame retardants (e.g., antimony trioxide); dispersants such as phosphate ester-based dispersants, polyoxyalkylene-based dispersants, acetylene-based dispersants, silicone-based dispersants, anionic dispersants, and cationic dispersants; stabilizers such as borate-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic anhydride-based stabilizers, etc. The content of the (G) component can be determined according to the properties required for the resin composition.

[0274] <(H) Organic solvent>

[0275] The resin composition of the present invention may further contain (H) an organic solvent as a volatile component. Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isopentyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, and diphenyl ether; alcohol solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; ether ester solvents such as 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, and methyl methoxypropionate; ester alcohol solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, and diethylene glycol monobutyl ether (butyl carbitol); amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane; and aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. The organic solvent may be used alone or in combination of two or more.

[0276] The resin composition of the present invention can be produced, for example, by adding component (A), component (B1), component (B2), and, if necessary, component (B3), component (C), component (D), component (E), component (F), component (G), or component (H) in any order and / or partially or entirely simultaneously in an arbitrary preparation container and mixing them. In addition, during the addition and mixing of each component, the temperature can be appropriately set, and heating and / or cooling can be performed temporarily or continuously. Further, during or after the addition and mixing, the resin composition can be stirred or shaken using a stirring device or an oscillating device such as a mixer to make it uniformly dispersed. In addition, defoaming can be performed under low-pressure conditions such as under vacuum while stirring or shaking.

[0277] [Physical properties and uses of the resin composition]

[0278] As described above, the resin composition of the present invention containing component (A) and component (B), and component (B) containing component (B1) and component (B2) can provide a cured product that exhibits good dielectric properties and, at the same time, good stain removability and excellent adhesion strength to the conductor layer.

[0279] The cured product of the resin composition of the present invention exhibits the characteristic of low relative dielectric constant (Dk). Therefore, by using this cured product, an insulating layer with a low relative dielectric constant is provided. For example, as described in the <Test Example 1: Measurement of Relative Dielectric Constant (Dk) and Dissipation Factor (Df)> column to be described later, when measured at 5.8 GHz and 23 °C, the relative dielectric constant of the cured product obtained by thermally curing the resin composition at 190 °C for 90 minutes is preferably 4.0 or less, more preferably 3.8 or less, and further preferably 3.5 or less. The lower limit value of the relative dielectric constant can be set to 0.001 or more, etc.

[0280] The cured product of the resin composition of the present invention exhibits the characteristic of low dissipation factor (Df). Therefore, by using this cured product, an insulating layer with a low dissipation factor is provided. For example, as described in the <Test Example 1: Measurement of Relative Dielectric Constant (Dk) and Dissipation Factor (Df)> column to be described later, when measured at 5.8 GHz and 23 °C, the dissipation factor of the cured product obtained by thermally curing the resin composition at 190 °C for 90 minutes is preferably 0.005 or less, more preferably 0.004 or less, and further preferably 0.003 or less. The lower limit value of the dissipation factor can be set to 0.001 or more, etc.

[0281] The cured product of the resin composition of the present invention exhibits excellent stain removability. As the maximum stain length of the cured product, it is preferably less than 5 μm, more preferably less than 2 μm. The lower limit of the maximum stain length of the cured product can be 0 μm or greater than 0 μm. The "maximum stain length" means the maximum length of the stain from the circumference of the bottom surface of the via (ビア) toward the center of the circle. The evaluation of the above maximum stain length can be measured according to the method described in the <Test Example 2: Evaluation of Stain Removability> column to be described later.

[0282] The insulating layer formed from the cured product of the resin composition of the present invention exhibits excellent adhesion strength (peel strength) with the conductor layer. As the adhesion strength, it is preferably 0.55 kgf / cm or more, more preferably 0.60 kgf / cm or more, and further preferably 0.65 kgf / cm or more. The higher the upper limit of the adhesion strength, the more preferable, and it can be set to, for example, 10 kgf / cm or less, etc. The measurement of the adhesion strength (peel strength) can be measured according to the method described in the <Test Example 3: Measurement of Adhesion Strength (Peel Strength) with Conductor Layer> column to be described later.

[0283] The resin composition of the present invention can exhibit excellent flexibility. Therefore, by using the resin composition of the present invention, a resin sheet excellent in flexibility can be manufactured. For example, a resin sheet is obtained by forming a resin composition layer on a plastic film as a support. When the resin sheet is bent 90° along a 3-mm diameter axis with the support on the inner side, breakage of the resin composition layer can be suppressed. The flexibility can be specifically measured according to the method described in <Test Example 4: Evaluation of Flexibility> below.

[0284] As described above, the resin composition of the present invention can provide a cured product that exhibits good dielectric properties and, at the same time, good stain removability and excellent adhesion strength to a conductor layer. 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 (resin composition for insulating layer of printed wiring board), and can be more suitably used as a resin composition for forming an interlayer insulating layer of a printed wiring board (resin composition for interlayer insulating layer of printed wiring board). The resin composition of the present invention can also be suitably used in the case where the printed wiring board is a board with components embedded. In addition, the resin composition of the present invention can be suitably used as a resin composition for forming an insulating layer of a redistribution substrate of a semiconductor package (resin composition for insulating layer of redistribution substrate). It should be noted that in the present invention, the printed wiring board and the redistribution substrate are collectively referred to as "circuit board", so the resin composition of the present invention can be suitably used as an insulating layer for a circuit board.

[0285] Furthermore, the resin composition of the present invention can be widely used in applications that require a resin composition, such as sheet-like laminated materials such as resin sheets and prepregs, solder masks, underfill materials, chip bonding materials, via filling resins, encapsulation resins, and component embedding resins.

[0286] [Sheet-like laminated materials (resin sheets, prepregs)]

[0287] The resin composition of the present invention can be used directly or in the form of a sheet-like laminated material containing the resin composition.

[0288] As the sheet-like laminated material, resin sheets and prepregs shown below are preferred.

[0289] In one embodiment, the resin sheet includes a support and a layer of the resin composition provided on the support (hereinafter, simply referred to as "resin composition layer"), and the resin composition layer is characterized by being formed of the resin composition of the present invention.

[0290] The thickness of the resin composition layer preferably varies depending on the use and can be appropriately determined according to the use. For example, from the viewpoint of thinning of printed wiring boards and semiconductor packages, the thickness of the resin composition layer is preferably 100 μm or less, 80 μm or less, 60 μm or less, 50 μm or less, 40 μm or less, or 30 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited and can generally be set to 1 μm or more, 5 μm or more, etc.

[0291] Examples of the support include a thermoplastic resin film, a metal foil, and a release paper, and a thermoplastic resin film and a metal foil are preferred. Therefore, in a preferred embodiment, the support is a thermoplastic resin film or a metal foil.

[0292] 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), polycarbonate (PC), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, and polyimide. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

[0293] When a metal foil is used as the support, examples of the metal foil include a copper foil and an aluminum foil, and a copper foil is preferred. As the copper foil, a foil formed of single metal of copper or a foil formed of an alloy of copper and other metals (such as tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) can be used.

[0294] The support can be subjected to matting treatment, corona treatment, or antistatic treatment on the surface that is joined to the resin composition layer. In addition, as the support, a support with a release layer on the surface that is joined to the resin composition layer can be used. Examples of the release agent used in the release layer of the support with a release layer include one or more release agents selected from alkyd resins, polyolefin resins, polyurethane resins, and silicone resins. Examples of commercially available products of the release agent include "SK-1", "AL-5", "AL-7", etc. manufactured by LINTEC Corporation as alkyd resin-based release agents. In addition, examples of commercially available products of the support with a release layer include PET films having a release layer mainly composed of an alkyd resin-based release agent, that is, "SK-1", "AL-5", "AL-7" manufactured by LINTEC Corporation, "Lumirror T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Limited, and "Unipeel" manufactured by UNITIKA Ltd.

[0295] The thickness of the support is not particularly limited, and is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. It should be noted that when using a support with a release layer, it is preferred that the overall thickness of the support with the release layer is within the above range.

[0296] When using a metal foil as the support, a metal foil with a support substrate, which is formed by laminating a peelable support substrate on a thin metal foil, can also be used. In one embodiment, the metal foil with a support substrate includes a support substrate, a release layer provided on the support substrate, and a metal foil provided on the release layer. When using the metal foil with a support substrate as the support, the resin composition layer is provided on the metal foil.

[0297] In the metal foil with a support substrate, the material of the support substrate is not particularly limited, and examples thereof include copper foil, aluminum foil, stainless steel foil, titanium foil, copper alloy foil, etc. When using a copper foil as the support substrate, it can be an electrolytic copper foil or a rolled copper foil. In addition, the release layer is not particularly limited as long as it can peel the metal foil from the support substrate, and examples thereof include an alloy layer of elements selected from Cr, Ni, Co, Fe, Mo, Ti, W, P; an organic coating film, etc.

[0298] In the metal foil with a support substrate, as the material of the metal foil, copper foil and copper alloy foil are preferred, for example.

[0299] In the metal foil with a support substrate, the thickness of the support substrate is not particularly limited, and is preferably in the range of 10 μm to 150 μm, more preferably in the range of 10 μm to 100 μm. In addition, the thickness of the metal foil can be set in the range of 0.1 μm to 10 μm, for example.

[0300] In one embodiment, the resin sheet can further optionally include any layer as needed. 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 (i.e., the surface on the opposite side of the support). The thickness of the protective film is not particularly limited, and is, for example, 1 μm to 40 μm. By laminating the protective film, the adhesion of dust, etc. on the surface of the resin composition layer or the generation of scratches can be suppressed.

[0301] The resin sheet can be manufactured, for example, by directly applying a liquid resin composition or preparing a resin varnish by dissolving the resin composition in an organic solvent, and then applying the prepared resin varnish onto the support using a die coater or the like, and further drying to form a resin composition layer.

[0302] Examples of the organic solvent include the same ones as those described as components of the resin composition. The organic solvent can be used alone or in combination of two or more.

[0303] Drying can be carried out by known methods such as heating and blowing hot air. The drying conditions are not particularly limited, and drying is carried out in such a way that the content of the organic solvent in the resin composition layer reaches 10% by mass or less, preferably 5% by mass or less. It also varies 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% to 60% by mass of the organic solvent, a resin composition layer can be formed by drying at 50°C to 150°C for 3 minutes to 10 minutes.

[0304] The resin sheet can be stored in a rolled state. When the resin sheet has a protective film, the resin sheet can be used by peeling off the protective film.

[0305] In one embodiment, the prepreg is formed by impregnating a sheet-like fiber substrate with the resin composition of the present invention.

[0306] The sheet-like fiber substrate used in the prepreg is not particularly limited, and materials commonly used as prepreg substrates such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric can be used. From the viewpoint of thinning the printed wiring board and semiconductor chip package, the thickness of the sheet-like fiber substrate is preferably 50 μm or less, more preferably 40 μm or less, further preferably 30 μm or less, and particularly preferably 20 μm or less. The lower limit of the thickness of the sheet-like fiber substrate is not particularly limited. Usually, it is 10 μm or more.

[0307] The prepreg can be manufactured by known methods such as the hot melt method and the solvent method.

[0308] The thickness of the prepreg can be set within the same range as the resin composition layer in the above resin sheet.

[0309] The sheet-like laminated material of the present invention can be suitably used for forming an insulating layer of a printed wiring board (for the insulating layer of a printed wiring board), and can be more suitably used for forming an interlayer insulating layer of a printed wiring board (for the interlayer insulating layer of a printed wiring board). In addition, the sheet-like laminated material of the present invention can also be suitably used for forming an insulating layer of a redistribution substrate of a semiconductor package (for the insulating layer of a redistribution substrate). That is, the sheet-like laminated material of the present invention can be suitably used as an insulating layer for a circuit board.

[0310] [Circuit board]

[0311] The insulating layer of the circuit board can be formed using the resin composition of the present invention. The present invention also provides the above circuit board, that is, a circuit board including an insulating layer formed of a cured product of the resin composition of the present invention.

[0312] <Printed wiring board>

[0313] In one embodiment, the circuit board of the present invention is a printed wiring board.

[0314] The printed wiring board can be manufactured, for example, by using the above resin sheet and a method including the following steps (I) and (II).

[0315] (I) A step of laminating a resin sheet on an inner layer substrate so that the resin composition layer of the resin sheet is joined to the inner layer substrate

[0316] (II) A step of curing (e.g., thermally curing) the resin composition layer to form an insulating layer

[0317] The "inner layer substrate" used in step (I) refers to a member that is a substrate of a printed wiring board. Examples thereof include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, etc. In addition, the substrate may have a conductor layer on one or both sides thereof, and the conductor layer may be patterned. An inner layer substrate having a conductor layer (circuit) formed on one or both sides of the substrate is sometimes referred to as an "inner layer circuit substrate". In addition, in the manufacture of a printed wiring board, an intermediate product for further forming an insulating layer and / or a conductor layer is also included in the "inner layer substrate" as referred to in the present invention. When the printed wiring board is a component-embedded circuit board, an inner layer substrate having components embedded therein can also be used.

[0318] The lamination of the inner layer substrate and the resin sheet can be carried out, for example, by thermocompression bonding the resin sheet to the inner layer substrate from the support side. As a member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter, also referred to as "thermocompression bonding member"), examples thereof include a heated metal plate (such as a SUS mirror surface plate) or a metal roll (SUS roll). It should be noted that the thermocompression bonding member can be directly pressed on the resin sheet, or can be pressed via an elastic material such as heat-resistant rubber so that the resin sheet can fully follow the surface unevenness of the inner layer substrate.

[0319] The lamination of the inner layer substrate and the resin sheet can be carried out by a vacuum lamination method. In the vacuum lamination method, the thermocompression bonding temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, the thermocompression bonding pressure is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably in the range of 0.29 MPa to 1.47 MPa, and the thermocompression bonding time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. The lamination can preferably be carried out under a reduced pressure condition of 26.7 hPa or less.

[0320] The lamination can be carried out by a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressure laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum coater manufactured by Nikko-Materials Co., Ltd., an intermittent vacuum pressure laminator, etc.

[0321] After lamination, by pressing the heat-bonding member from the support side under normal pressure (atmospheric pressure), for example, smoothing treatment of the laminated resin sheets can be performed. The pressing conditions for the smoothing treatment can be set to the same conditions as the above-described heat-bonding conditions for lamination. The smoothing treatment can be performed using a commercially available laminator. It should be noted that lamination and smoothing treatment can be continuously performed using the above-described commercially available vacuum laminator.

[0322] The support can be removed between step (I) and step (II), or can be removed after step (II). It should be noted that when using a metal foil as the support, the metal foil can also be used to form a conductor layer without peeling off the support. In addition, when using a metal foil with a support substrate as the support, it is only necessary to peel off the support substrate (and the release layer). Subsequently, a conductor layer can be formed using the metal foil.

[0323] In step (II), the resin composition layer is cured (for example, thermally cured) to form an insulating layer formed of a cured product of the resin composition. The curing conditions of the resin composition layer are not particularly limited, and conditions generally employed when forming an insulating layer of a printed wiring board can be used.

[0324] For example, the thermal curing conditions of the resin composition layer vary depending on the type of the resin composition, etc. In one embodiment, the curing temperature is preferably 140°C to 250°C, more preferably 150°C to 240°C, and further preferably 160°C to 230°C. The curing time can be set to preferably 5 minutes to 240 minutes, more preferably 10 minutes to 150 minutes, and further preferably 15 minutes to 120 minutes.

[0325] Before thermally curing the resin composition layer, the resin composition layer can be preheated at a temperature lower than the curing temperature. For example, before thermally curing the resin composition layer, the resin composition layer can be preheated 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, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and further preferably 15 minutes to 100 minutes.

[0326] When manufacturing a printed wiring board, the steps of (III) opening holes in the insulating layer, (IV) roughening the insulating layer, and (V) forming a conductor layer can be further implemented. These steps (III) to (V) can be implemented according to various methods well-known to those skilled in the art used in the manufacture of printed wiring boards. It should be noted that when removing the support after step (II), the removal of the support can be implemented between step (II) and step (III), between step (III) and step (IV), or between step (IV) and step (V). In addition, the formation of the insulating layer and the conductor layer in steps (I) to (V) can be repeatedly implemented as needed to form a multilayer wiring board.

[0327] In other embodiments, the printed wiring board of the present invention can be manufactured using the above prepreg. The manufacturing method is basically the same as that in the case of using a resin sheet.

[0328] Step (III) is the step of opening holes in the insulating layer, whereby holes such as vias and through-holes can be formed in the insulating layer. Step (III) can be implemented using, for example, a drill, a laser, a plasma, etc., according to the composition of the resin composition used in the formation of the insulating layer. The size and shape of the holes can be appropriately determined according to the design of the printed wiring board.

[0329] Step (IV) is the step of roughening the insulating layer. Usually, stain removal (de-staining) is also performed in this step (IV). The steps and conditions for the roughening treatment are not particularly limited, and known steps and conditions commonly used in the formation of the insulating layer of a printed wiring board can be adopted. For example, the insulating layer can be roughened by sequentially performing a swelling treatment using a swelling liquid, a roughening treatment using an oxidizing agent, and a neutralization treatment using a neutralizing liquid.

[0330] The swelling liquid used in the roughening treatment is not particularly limited, and examples include an alkali solution and a surfactant solution. An alkali solution is preferred, and as the alkali solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferred. Examples of commercially available swelling liquids include "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by ATOTECH JAPAN Co., Ltd. The swelling treatment using the swelling liquid is not particularly limited. For example, it can be performed by immersing the insulating layer in the swelling liquid at 30°C to 90°C for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferred to immerse the insulating layer in the swelling liquid at 40°C to 80°C for 5 minutes to 15 minutes.

[0331] As the oxidizing agent used in the roughening treatment, there is no particular limitation, and examples thereof include an alkaline permanganic acid solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. The roughening treatment using an oxidizing agent such as an alkaline permanganic acid solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated to 60°C to 100°C for 10 minutes to 30 minutes. In addition, the concentration of the permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. As commercially available oxidizing agents, for example, alkaline permanganic acid solutions such as "Concentrate Compact CP", "Concentrate Compact P", and "Dosing Solution Securiganth P" manufactured by ATOTECH JAPAN Co., Ltd. can be cited.

[0332] In addition, as the neutralizing solution used in the roughening treatment, an acidic aqueous solution is preferred. As commercially available products, for example, "Reduction Solution Securiganth P" manufactured by ATOTECH JAPAN Co., Ltd. can be cited.

[0333] The treatment using the neutralizing solution can be carried out by immersing the treated surface that has undergone the roughening treatment using the oxidizing agent in the neutralizing solution at 30°C to 80°C for 5 minutes to 30 minutes. From the viewpoints of operability and the like, a method of immersing the object to be roughened using the oxidizing agent in the neutralizing solution at 40°C to 70°C for 5 minutes to 20 minutes is preferred.

[0334] Step (V) is a step of forming a conductor layer, and a conductor layer is formed on the insulating layer. There is no particular limitation on the conductor material used in the conductor layer. In a preferred embodiment, the conductor layer contains one or more metals selected from gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductor layer can be a single-metal layer or an alloy layer. Examples of the alloy layer include a layer formed of an alloy of two or more metals selected from the above (for example, nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy). Among them, from the viewpoints of the versatility of conductor layer formation, cost, ease of patterning, etc., a single-metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy, copper-nickel alloy, or copper-titanium alloy is preferred, and a single-metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy is more preferred, and a single-metal layer of copper is further preferred.

[0335] Even when the conductor layer has a single-layer structure, it can be a multi-layer structure obtained by laminating two or more single-metal layers or alloy layers formed of different metals or alloys. When the conductor layer has a multi-layer 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.

[0336] The thickness of the conductor layer depends on the design of the printed wiring board desired, and is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

[0337] In one embodiment, the conductor layer can be formed by plating. From the viewpoint of easily forming fine wirings, it is preferably formed by the semi-additive method. Hereinafter, an example of forming a conductor layer by the semi-additive method will be shown.

[0338] First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern corresponding to the desired wiring pattern and exposing a part of the plating seed layer is formed on the formed plating seed layer. After forming a metal layer by electroplating on the exposed plating seed layer, the mask pattern is removed. Then, the unnecessary plating seed layer is removed by etching or the like, and a conductor layer having the desired wiring pattern can be formed.

[0339] In other embodiments, the conductor layer can be formed using a metal foil. When forming the conductor layer using a metal foil, step (V) is preferably carried out between step (I) and step (II). For example, after removing the support in step (I), the metal foil is laminated on the surface of the exposed resin composition layer. The lamination of the resin composition layer and the metal foil can be carried out by a vacuum lamination method. The lamination conditions can be set to be the same as those described for step (I). Next, step (II) is carried out to form the insulating layer. Then, using the metal foil on the insulating layer, a conductor layer having the desired wiring pattern can be formed by a conventionally known technique such as a modified semi-additive method.

[0340] The metal foil can be manufactured by a conventionally known method such as an electrolytic method or a rolling method. As commercially available products of the metal foil, for example, HLP foil, JXUT-III foil manufactured by JX Metals Co., Ltd., 3EC-III foil, TP-III foil manufactured by Metal Mining Co., Ltd., etc. can be cited.

[0341] Alternatively, when using a metal foil or a metal foil with a support substrate as the support of the resin sheet, the conductor layer can also be formed using the metal foil as described above.

[0342] <Re-wiring substrate of semiconductor package>

[0343] In one embodiment, the circuit substrate of the present invention is a re-wiring substrate (re-wiring layer) of a semiconductor package. Hereinafter, a method for manufacturing a semiconductor package will be described.

[0344] The semiconductor package includes an insulating layer formed of a cured product of the resin composition of the present invention as the insulating layer of the re-wiring substrate. It should be noted that the semiconductor package may also include a sealing layer formed of a cured product of the resin composition of the present invention.

[0345] A semiconductor package can be manufactured, for example, by using the resin composition and resin sheet of the present invention through a method including the following steps (1) to (6). The resin composition and resin sheet of the present invention can be used to form the rewiring formation layer (insulating layer for forming a rewiring substrate) in step (5) or the sealing layer in step (3). Hereinafter, an example of forming the rewiring formation layer and the sealing layer using the resin composition and resin sheet is shown. However, the technology for forming the rewiring formation layer and the sealing layer of a semiconductor package is well-known, and those skilled in the art can use the resin composition and resin sheet of the present invention to manufacture a semiconductor package according to the well-known technology.

[0346] (1) A step of laminating a temporary fixing film on a substrate;

[0347] (2) A step of temporarily fixing a semiconductor chip on the temporary fixing film;

[0348] (3) A step of forming a sealing layer on the semiconductor chip;

[0349] (4) A step of peeling the substrate and the temporary fixing film from the semiconductor chip;

[0350] (5) A step of forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the substrate and the temporary fixing film have been peeled; and

[0351] (6) A step of forming a rewiring layer as a conductor layer on the rewiring formation layer.

[0352] - Step (1) -

[0353] The material for the substrate is not particularly limited. Examples of the substrate include semiconductor wafers such as silicon wafers; glass wafers; glass substrates; metal substrates such as copper, titanium, stainless steel, and cold-rolled steel sheets (SPCC); substrates obtained by impregnating glass fibers with epoxy resins and performing thermosetting treatment (e.g., FR-4 substrates); substrates formed of bismaleimide triazine resins (BT resins), etc.

[0354] The material of the temporary fixing film is not particularly limited as long as it can be peeled from the semiconductor chip in step (4) and can temporarily fix the semiconductor chip. Commercially available products can be used as the temporary fixing film. Examples of commercially available products include REVALPHA manufactured by Nitto Denko Corporation.

[0355] - Step (2) -

[0356] The temporary fixing of the semiconductor chip can be performed using well-known devices such as a flip chip bonder and a chip bonder. The layout and the number of configurations of the semiconductor chips can be appropriately set according to the shape and size of the temporary fixing film, the production quantity of the target semiconductor package, etc. For example, they can be arranged and temporarily fixed in a matrix of multiple rows and multiple columns.

[0357] - Step (3)-

[0358] The resin composition of the resin sheet of the present invention is laminated layer by layer on a semiconductor chip, or the resin composition of the present invention is coated on a semiconductor chip and cured (for example, thermally cured) to form a sealing layer.

[0359] For example, the lamination of the semiconductor chip and the resin sheet can be carried out by removing the protective film of the resin sheet and then thermocompression bonding the resin sheet to the semiconductor chip from the support side. As a member for thermocompression bonding the resin sheet to the semiconductor chip (hereinafter, also referred to as "thermocompression bonding member"), for example, a heated metal plate (such as a SUS mirror surface plate) or a metal roller (such as a SUS roller) can be cited. It should be noted that the thermocompression bonding member is not directly pressed on the resin sheet, but it is preferably pressed via an elastic material such as heat-resistant rubber so that the resin sheet can fully follow the surface unevenness of the semiconductor chip. The lamination of the semiconductor chip and the resin sheet can be carried out by the vacuum lamination method, and the lamination conditions are the same as those described for the manufacturing method of the printed wiring board, and the preferred ranges are also the same.

[0360] After lamination, the resin composition is thermally cured to form a sealing layer. The thermal curing conditions are the same as those described for the thermal curing of the printed wiring board manufacturing method.

[0361] The support of the resin sheet can be peeled off after laminating the resin sheet on the semiconductor chip and thermally curing it, or the support can be peeled off before laminating the resin sheet on the semiconductor chip.

[0362] When coating the resin composition of the present invention to form a sealing layer, as the coating conditions, they are the same as those for forming the resin composition layer described for the resin sheet of the present invention, and the preferred ranges are also the same.

[0363] - Step (4)-

[0364] The method of peeling the base material and the temporary fixing film can be appropriately changed according to the material of the temporary fixing film, etc. For example, methods such as heating, foaming (or expanding) the temporary fixing film to peel it off, and irradiating ultraviolet rays from the base material side to reduce the adhesive force of the temporary fixing film to peel it off can be cited.

[0365] In the method of heating, foaming (or expanding) the temporary fixing film to peel it off, the heating conditions are usually 1 to 90 seconds or 5 to 15 minutes at 100 to 250 °C. In addition, in the method of irradiating ultraviolet rays from the base material side to reduce the adhesive force of the temporary fixing film to peel it off, the irradiation amount of ultraviolet rays is usually 10 mJ / cm 2 ~1000 mJ / cm 2 .

[0366] - Step (5)-

[0367] The resin composition and resin sheet of the present invention are used to form a redistribution formation layer (insulating layer of the redistribution substrate).

[0368] After forming the redistribution formation layer, in order to perform interlayer connection between the semiconductor chip and the conductor layer described later, vias can also be formed in the redistribution formation layer. The vias can be formed by a known method according to the material of the redistribution formation layer.

[0369] - Step (6)-

[0370] The formation of the conductor layer on the redistribution formation layer can be carried out in the same manner as step (V) described in the manufacturing method of printed wiring boards. It should be noted that steps (5) and (6) can be repeated to alternately stack (build up) the conductor layer (redistribution layer) and the redistribution formation layer (insulating layer).

[0371] When manufacturing a semiconductor package, steps (7) of forming a solder resist layer on the conductor layer (redistribution layer), (8) of forming bumps, and (9) of singulating a plurality of semiconductor packages into individual semiconductor packages can be further implemented. These steps can be carried out according to various methods well-known to those skilled in the art used in the manufacturing of semiconductor packages.

[0372] By using the resin composition and resin sheet of the present invention that can provide a cured product exhibiting good dielectric properties, good stain removability, and excellent adhesion strength to the conductor layer to form the redistribution formation layer (insulating layer), a semiconductor package with extremely low transmission loss can be achieved regardless of whether the semiconductor package is a Fan-In type package or a Fan-Out type package. In one embodiment, the semiconductor package of the present invention is a Fan-Out type package. The resin composition and resin sheet of the present invention are applicable to both Fan-Out Panel Level Packaging (FOPLP) and Fan-Out Wafer Level Packaging (FOWLP). In one embodiment, the semiconductor package of the present invention is Fan-Out Panel Level Packaging (FOPLP) or Fan-Out Wafer Level Packaging (FOWLP).

[0373] [Semiconductor device]

[0374] The semiconductor device of the present invention includes a layer composed 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 circuit board of the present invention.

[0375] Examples of the semiconductor device include various semiconductor devices used in electrical products (such as computers, mobile phones, digital cameras, and televisions, etc.) and transportation means (such as motorcycles, automobiles, trams, ships, and airplanes, etc.).

[0376] Example

[0377] Hereinafter, examples will be shown to specifically describe the present invention. However, the present invention is not limited to these examples. In the following description, "parts" and "%" indicating amounts mean "parts by mass" and "mass %", respectively, unless otherwise specified. In addition, the temperature conditions and pressure conditions are room temperature (23 °C) and atmospheric pressure (1 atm) unless otherwise specified.

[0378] <Synthesis Example 1: Synthesis of Active Ester Resin B (Active Ester Resin Containing Specific Structural Unit)>

[0379] In a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube, and a stirrer, 320 g (2.0 moles) of 2,7-dihydroxynaphthalene, 184 g (1.7 moles) of benzyl alcohol, and 5.0 g of p-toluenesulfonic acid monohydrate were added, and while blowing nitrogen at room temperature, the mixture was stirred. Then, the temperature was raised to 150 °C, and while distilling the generated water out of the system, stirring was carried out for 4 hours. After the reaction was completed, 900 g of methyl isobutyl ketone and 5.4 g of 20% aqueous sodium hydroxide solution were added for neutralization, and then the aqueous layer was removed by liquid separation. The mixture was washed three times with 280 g of water, and methyl isobutyl ketone was removed under reduced pressure to obtain 460 g of benzyl-modified naphthalene compound A. The obtained benzyl-modified naphthalene compound A was a black solid, and the hydroxyl equivalent was 180 g / equivalent.

[0380] In a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube, and a stirrer, 203.0 g (the number of moles of acyl chloride group: 2.0 moles) of isophthaloyl chloride and 1400 g of toluene were added, and the inside of the system was purged with nitrogen under reduced pressure to dissolve it. Then, 113.9 g (0.67 moles) of o-phenylphenol and 240 g (the number of moles of phenolic hydroxyl group: 1.33 moles) of benzyl-modified naphthalene compound A were added, and the inside of the system was purged with nitrogen under reduced pressure to dissolve it. Then, 0.70 g of tetrabutylammonium bromide was dissolved, nitrogen purging was applied, and the temperature inside the system was controlled below 60 °C. 400 g of 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. Then, stirring was continued for 1.0 hour under this condition. After the reaction was completed, the mixture was allowed to stand for liquid separation to remove the aqueous layer. Further, water was added to the toluene layer in which the reactants were dissolved, and the mixture was stirred and mixed for 15 minutes, allowed to stand for liquid separation, and the aqueous layer was removed. This operation was repeated until the pH of the aqueous layer reached 7. Then, the water was removed by dehydration with a decanter to obtain an active ester resin B in a toluene solution state with a non-volatile content of 65% by mass. The active ester equivalent of the obtained active ester resin B was 238 g / eq. The obtained active ester resin B is represented by the following formula (wherein, mainly composed of compounds in which n is an integer from 0 to 5 and m is an integer from 0 to 15).

[0381] [Chemical Formula 14]

[0382]

[0383] <Synthesis Example 2: Synthesis Example of Active Ester Resin C (Active Ester Resin Containing Allyl Group)>

[0384] In a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating column, and a stirrer, 165 g of a polyaddition reaction resin of dicyclopentadiene and phenol (hydroxyl equivalent: 165 g / eq., softening point 85°C), 134 g (1.0 mol) of o-allylphenol, and 1200 g of toluene were added, and the system was purged with nitrogen under reduced pressure. Subsequently, 203 g (1.0 mol) of isophthaloyl chloride was added, and the system was purged with nitrogen under reduced pressure. 0.6 g of tetrabutylammonium bromide was added, and while performing a nitrogen purge treatment, the temperature inside the system was controlled below 60°C, and 41.2 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After the addition was completed, the mixture was stirred for 1 hour. After the reaction was completed, the aqueous layer was removed by standing and separating. Water was further added to the obtained toluene layer, and the mixture was stirred for 15 minutes, and the aqueous layer was removed by standing and separating. This operation was repeated until the pH of the aqueous layer reached 7. Subsequently, the non-volatile content was adjusted to 70% by mass by heating and drying, thereby obtaining the active ester resin C represented by the following chemical formula.

[0385] [Chemical Formula 15]

[0386]

[0387] In the above chemical formula, s are each independently an integer of 0 or 1 or more, and the average value of r calculated from the addition ratio is 1. In addition, the dotted line in the chemical formula is a structure obtained by the reaction of isophthaloyl chloride, and the polyaddition reaction resin of phenol and / or o-allylphenol. The ester group equivalent of the active ester resin C calculated from the addition ratio was 214 g / eq.

[0388] <Examples 1 to 10 and Comparative Examples 1 to 5. Preparation of Resin Varnish>

[0389] Weigh and mix each component in the amounts (parts by mass) described in Tables 1 and 2 below, and further mix 10 parts by mass of methyl ethyl ketone and 10 parts by mass of cyclohexanone, and disperse them uniformly using a high-speed rotary mixer to obtain a varnish-like resin composition (resin varnish). The details of each component described in Tables 1 and 2 below are as follows.

[0390] (A) Epoxy resin:

[0391] · "HP-4032-SS": Manufactured by DIC Corporation, naphthalene-type liquid epoxy resin, epoxy equivalent 144 g / eq.

[0392] · "NC-3000L": A naphthol novolak type solid epoxy resin manufactured by Nippon Kayaku Co., Ltd., with an epoxy equivalent of 272 g / eq.

[0393] (B1) Active ester resin containing specific structural units:

[0394] · "HPC-8150-62T": An active ester resin manufactured by DIC Corporation, containing the structural unit shown in formula (B1-1), i.e., the active ester resin shown in formula (B1-3) (in formula (B1-3), Ar 1 is a naphthylene group having two benzyl groups as substituents, Ar 2 is a naphthyl group, R B is a phenylene group, m1 is 0, m2 is 1), a toluene solution with a non-volatile content of 61.5% by mass, and an active ester group equivalent of 223 g / eq.

[0395] · "Active Ester B": An active ester resin containing the structural unit shown in formula (B1-1) synthesized in Synthesis Example 1

[0396] (B2) Active ester resin containing allyl groups:

[0397] · "Active Ester C": An active ester resin containing allyl groups synthesized in Synthesis Example 2

[0398] · "Active Ester D": An active ester resin containing allyl groups, i.e., the active ester resin shown in the following formula (mainly composed of compounds where n is an integer from 0 to 6 and m is an integer from 0 to 6), a toluene solution with a non-volatile content of 70% by mass, and an active ester group equivalent of 250 g / eq.

[0399] [Chemical Formula 16]

[0400]

[0401] (B3) Other active ester resins:

[0402] · "HPC-8000L-65TM": An active ester resin manufactured by DIC Corporation, containing a dicyclopentadiene type diphenol structure, a toluene:methyl ethyl ketone = 1:1 solution with a non-volatile content of 65% by mass

[0403] (C) Inorganic filler:

[0404] · "SO-C2": Spherical silica (manufactured by Admatechs Co., Ltd.) surface-treated with an amine-based alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.)

[0405] (D) Other thermosetting resins:

[0406] · "LA-3018-50P": Manufactured by DIC Corporation, a phenol-based curing agent, a 1-methoxy-2-propanol solution with a non-volatile content of 50% by mass, and a phenol equivalent of 151 g / eq.

[0407] · "LA-1356": Manufactured by DIC Corporation, a phenol-based curing agent, a methyl ethyl ketone solution with a non-volatile content of 60% by mass, and a phenol equivalent of 146 g / eq.

[0408] (E) Organic filler:

[0409] · "EXL-2655": Manufactured by Dow Chemical Japan Co., Ltd., rubber particles

[0410] (F) Curing accelerator:

[0411] · "1B2PZ": Manufactured by Shikoku Kasei Kogyo Co., Ltd., an imidazole-based curing accelerator

[0412] [Table 1]

[0413] [Composition of the resin varnishes of Examples 1 to 7 in Table 1]

[0414]

[0415] [Table 2]

[0416] [Composition of the resin varnishes of Examples 8 to 10 and Comparative Examples 1 to 5 in Table 2]

[0417]

[0418] <Production of Resin Sheet A>

[0419] As a support, a polyethylene terephthalate film with a release layer (LINTEC Corporation's "AL5", thickness 38 μm) was prepared. The resin varnishes obtained in the examples and comparative examples were uniformly coated on the release layer of the support so that the thickness of the dried resin composition layer reached 40 μm. Then, the resin composition was dried at 80°C to 100°C (average 90°C) for 2 minutes to obtain Resin Sheet A containing the support and the resin composition layer.

[0420] <Test Example 1: Measurement of relative dielectric constant (Dk) and dissipation factor (Df)>

[0421] The Resin Sheet A obtained in the examples and comparative examples was cured in an oven at 190°C for 90 minutes. The support was peeled off from the Resin Sheet A taken out of the oven, and thus a cured product of the resin composition layer was obtained. This cured product was cut into a length of 80 mm and a width of 2 mm as the cured product for evaluation.

[0422] For each cured product for evaluation, using "HP8362B" manufactured by Agilent Technologies, the values of dielectric constant and dielectric loss tangent (Dk value · Df value) were measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23 °C by the cavity resonance perturbation method. The measurement was carried out with two test pieces, and the average value was calculated.

[0423] <Test Example 2: Evaluation of stain removability>

[0424] (1) Substrate treatment of the inner layer circuit board

[0425] Both sides of a glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, "R1515A" manufactured by Panasonic Corporation) with an inner layer circuit formed were etched with a micro-etchant ("CZ8101" manufactured by MEC Corporation) by 1 μm to roughen the copper surface.

[0426] (2) Lamination of resin sheets

[0427] Using an intermittent vacuum pressure laminator (two-stage incremental lamination machine "CVP700" manufactured by Nikko-Materials), resin sheet A was laminated on both sides of the inner layer substrate in such a way that the resin composition layer was in contact with the inner layer substrate. This lamination was carried out by adjusting the air pressure to 13 hPa or less by decompression for 30 seconds and then performing a pressure bonding for 30 seconds at 120 °C and a pressure of 0.74 MPa. Then, a hot press was carried out at 100 °C and a pressure of 0.5 MPa for 60 seconds.

[0428] (3) Thermal curing of the resin composition layer

[0429] The inner layer substrate laminated with resin sheet A was put into an oven at 130 °C and heated for 30 minutes, and then transferred to an oven at 170 °C and heated for 30 minutes to thermally cure the resin composition layer and form an insulating layer. Then, the support was peeled off to obtain a cured substrate A1 having an insulating layer / inner layer substrate / insulating layer in sequence.

[0430] (4) Formation of vias

[0431] For the cured substrate A1, using a CO2 laser processing machine (LK-2K212 / 2C) manufactured by Via Mechanics, the insulating layer was processed under the conditions of a frequency of 2000 Hz, a pulse width of 3 μs, an output of 0.95 W, and a number of emissions of 3 to form vias with a top diameter (diameter) of 50 μm on the surface of the insulating layer and a diameter of 50 μm at the bottom of the insulating layer, obtaining a circuit board A2.

[0432] (5) Roughening treatment

[0433] The surface of the insulating layer of circuit board A2 was immersed in SwellingDipSecuriganth P of ATOTECH JAPAN Co., Ltd. as a swelling liquid at 60°C for 10 minutes. Subsequently, the surface of the insulating layer of the circuit board was immersed in Concentrate Compact P (aqueous solution of KMnO4: 60 g / L, NaOH: 40 g / L) of ATOTECH JAPAN Co., Ltd. as a roughening liquid at 80°C for 15 minutes. Finally, the surface of the insulating layer of the circuit board was immersed in Reduction Solution Securiganth P of ATOTECH JAPAN Co., Ltd. as a neutralizing liquid at 40°C for 5 minutes.

[0434] (6) Evaluation of stain removability

[0435] In the circuit board A2 after roughening treatment, the periphery of the bottom of the via hole was observed with a scanning electron microscope (SEM), and the maximum stain length starting from the wall surface of the bottom of the via hole was measured from the obtained image, and the evaluation was carried out according to the following criteria.

[0436] [Evaluation criteria for stain removability]

[0437] ◎: The maximum stain length is less than 2 μm

[0438] ○: The maximum stain length is 2 μm or more and less than 5 μm

[0439] ×: The maximum stain length is 5 μm or more

[0440] <Test Example 3: Determination of the adhesion strength (peel strength) with the conductor layer>

[0441] (1) Substrate treatment of the substrate for adhesion strength evaluation

[0442] As an inner layer substrate, a glass cloth-based epoxy resin double-sided copper-clad laminate with a copper foil on the surface (copper foil thickness 18 μm, substrate thickness 0.8 mm, "R1515A" manufactured by Panasonic Corporation) was prepared. All the copper foils on the surface of the inner layer substrate were etched away. Then, it was dried at 190°C for 30 minutes.

[0443] (2) Lamination of resin sheets

[0444] Using an intermittent vacuum pressure laminator (manufactured by Nikko-Materials Co., Ltd., two-stage incremental layer laminator "CVP700"), the resin sheet A was laminated to both sides of the inner substrate in such a way that the resin composition layer was in contact with the inner substrate. This lamination was carried out by reducing the pressure for 30 seconds to adjust the air pressure to 13 hPa or less, and then performing crimping at 100 °C and a pressure of 0.74 MPa for 30 seconds. Subsequently, hot pressing was performed at 100 °C and a pressure of 0.5 MPa for 60 seconds. Then, the support was peeled off to obtain an intermediate multilayer body I successively including a resin composition layer / inner substrate / resin composition layer.

[0445] (3) Substrate treatment of copper foil

[0446] The shiny surface of the electrolytic copper foil (manufactured by Mitsui Mining & Smelting Co., Ltd., "3EC-III", thickness 35 μm) was etched with a micro-etchant (manufactured by MEC Co., Ltd., "CZ8101") by 1 μm to roughen the copper surface, and then an anti-rust treatment (CL8300) was carried out. Hereinafter, the copper foil whose surface has been etched with the aforementioned micro-etchant is sometimes referred to as "CZ copper foil". Further, the copper foil was heat-treated in an oven at 130 °C for 30 minutes to obtain a copper foil I having a processed surface on which the roughening treatment has been carried out.

[0447] (4) Lamination of copper foil

[0448] The copper foil I was laminated to both sides of the intermediate multilayer body I in such a way that the processed surface of the copper foil I was joined to the resin composition layer of the intermediate multilayer body I. This lamination was carried out under the same conditions as in the above "(2) Lamination of resin sheet". Thereby, an intermediate multilayer body II successively including copper foil I / resin composition layer / inner substrate / resin composition layer / copper foil I was obtained.

[0449] (5) Thermal curing of resin composition layer

[0450] The intermediate multilayer body II was put into an oven at 100 °C and heated for 30 minutes, and then transferred to an oven at 170 °C and heated for 30 minutes. Then, the intermediate multilayer body II was taken out of the oven to the room temperature atmosphere, and then further put into an oven at 200 °C and heated additionally for 90 minutes. Thereby, the thermal curing of the resin composition layer was carried out to obtain an evaluation substrate III successively including roughened copper foil / insulating layer (cured product of resin composition layer) / inner substrate / insulating layer (cured product of resin composition layer) / roughened copper foil. In this evaluation substrate III, the roughened copper foil corresponds to the conductor layer.

[0451] (6) Measurement of adhesion strength (peel strength) with conductor layer

[0452] Using the evaluation substrate III, the peel strength between the roughened copper foil and the insulating layer was measured. The measurement of the peel strength was carried out in accordance with JIS C6481. Specifically, the measurement of the peel strength was performed by the following operations.

[0453] On the roughened copper foil of the evaluation substrate III, a cut was made to surround a rectangular portion with a width of 10 mm and a length of 100 mm. One end of this rectangular portion was peeled off and clamped with a jig (manufactured by TSE Corporation, AUTO COM type testing machine "AC-50C-SL"). The 35-mm length range of the aforementioned rectangular portion was peeled off in the vertical direction, and the load (kgf / cm) during this peeling was measured as the peel strength. The aforementioned peeling was carried out at a speed of 50 mm / minute at room temperature. Based on the measured values, the adhesion strength with the conductor layer was evaluated using the following criteria.

[0454] [Evaluation Criteria for Adhesion Strength with Conductor Layer]

[0455] ○: The value of the peel strength is 0.65 kgf / cm or more

[0456] △: The value of the peel strength is 0.55 kgf / cm or more and less than 0.65 kgf / cm

[0457] ×: The value of the peel strength is less than 0.55 kgf / cm

[0458] <Test Example 4: Evaluation of Flexibility>

[0459] The resin sheet A was bent 90° along a 3-mm diameter axis with the support body on the inside, and the flexibility was confirmed. The evaluation was carried out based on the following criteria.

[0460] [Evaluation Criteria for Flexibility]

[0461] ○: There is no rupture of the resin composition layer

[0462] ×: There is a rupture of the resin composition layer

[0463] <Results>

[0464] The results of the examples and comparative examples are shown in Tables 3 and 4 below.

[0465] [Table 3]

[0466] [Table 3. Results of Examples 1 to 7]

[0467]

[0468] [Table 4]

[0469] [Table 4. Results of Examples 8 to 10 and Comparative Examples 1 to 5]

[0470]

Claims

1. A resin composition comprising: (A) an epoxy resin, and (B) an active ester resin, The component (B) comprises: (B1) an active ester resin containing a structural unit represented by the following formula (B1-1), and (B2) an active ester resin containing an allyl group. [Chemistry 1] In formula (B1-1), Ar 1 Each independently represents a divalent aromatic group which may have a substituent; At least 1 Ar 1 is a naphthylene group which may have a substituent; L B Each independently represents a single bond or a divalent linking group; R B1 represents a divalent hydrocarbon group which may have a substituent, an oxygen atom, a sulfur atom, or a divalent group consisting of a combination thereof; m1 is an integer from 0 to 5; "*" indicates a bonding key.

2. The resin composition according to claim 1, wherein The quantitative ratio of the component (A) to the component (B) is in the range of 1:0.3 to 1:2 in terms of the ratio of [the total number of epoxy groups of the component (A)]:[the total number of active ester groups of the component (B)].

3. The resin composition according to claim 1, wherein When the resin component in the resin composition is 100 mass %, content of the component (A) is 20 mass % or more and 50 mass % or less.

4. The resin composition according to claim 1, wherein When the resin component in the resin composition is 100 mass %, content of the component (B1) is 10 mass % or more and 60 mass % or less.

5. The resin composition according to claim 1, wherein When the resin component in the resin composition is 100 mass %, content of the component (B2) is 10 mass % or more and 60 mass % or less. The resin composition according to claim 1 , further comprising (C) an inorganic filler.

7. The resin composition according to claim 6, wherein When the nonvolatile matter in the resin composition is 100 mass %, the content of the component (C) is 50 mass % or more and 90 mass % or less. The resin composition according to claim 1 , which is used for forming an insulating layer.

9. A resin sheet comprising a support and a resin composition layer provided on the support, The resin composition layer contains the resin composition according to any one of claims 1 to 8. 10 . A circuit board comprising a cured product of the resin composition according to claim 1 .

11. A semiconductor device comprising the circuit substrate according to claim 10.

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