Resin composition

Abstract

To provide a new resin composition which can provide a cured product that has a low dielectric loss tangent, exhibits good elongation, and is excellent in uniformity.SOLUTION: A resin composition contains an inorganic filler, an oligophenylene ether skeleton-containing resin X having a weight average molecular weight Mw represented by MC, and an oligophenylene ether skeleton-containing resin Y having a weight average molecular weight Mw represented by MD, wherein MC and MD satisfy the following condition 1. [Condition 1] 1,000,000>MC>5MD>500, or the resin composition contains an inorganic filler, an oligophenylene ether skeleton-containing resin X having a glass transition temperature of 25°C or lower and an oligophenylene ether skeleton-containing resin Y different from the resin X.SELECTED DRAWING: None

Description

[Technical field]

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

[0002] For insulating materials such as sealing materials for semiconductor chip packages and interlayer insulating materials for circuit boards, the need for low dielectric tangents is increasing for next-generation high-speed communications. Conventionally, resins having a PPE (polyphenylene ether) skeleton have been considered as a chemical structure with a low dielectric tangent (for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2022-39594 A Summary of the Invention [Problem to be solved by the invention]

[0004] Although resins with a PPE skeleton contribute to a low dielectric tangent, their stiffness (low elongation) and poor compatibility with other resins have been problems. It has been confirmed that such problems become more pronounced when inorganic fillers are mixed in large amounts to achieve a low dielectric tangent.

[0005] An object of the present invention is to provide a resin composition which has a low dielectric tangent, exhibits good elongation, and gives a cured product with excellent uniformity. [Means for solving the problem]

[0006] As a result of intensive research, the present inventors have found that the above problems can be solved by a resin composition having the following composition, which contains a combination of two or more types of resins containing a specific oligophenylene ether skeleton (hereinafter also referred to as "oligophenylene ether skeleton-containing resin"), and have thus completed the present invention.

[0007] That is, the present invention includes the following. [1] inorganic filler, An oligophenylene ether skeleton-containing resin X having a weight average molecular weight Mw of MC, and Oligophenylene ether skeleton-containing resin Y having a weight average molecular weight Mw of MD wherein MC and MD satisfy the following condition 1. <Condition 1>1,000,000>MC>5MD>500 [2] inorganic filler, An oligophenylene ether skeleton-containing resin X having a glass transition temperature of 25° C. or lower, and Resin Y containing an oligophenylene ether skeleton different from Resin X A resin composition comprising: [3] The resin composition according to [1] or [2], wherein the total content of resin X and resin Y is 20% by mass or more and less than 70% by mass, when the resin component in the resin composition is 100% by mass. [4] The resin composition according to any one of [1] to [3], wherein the content of the inorganic filler is 50% by mass or more when the non-volatile components in the resin composition are taken as 100% by mass. [5] The resin composition according to any one of [1] to [4], wherein Resin X contains one or more structural units selected from the group consisting of polyolefin structural units, polycarbonate structural units, polyether structural units, polyester structural units, poly(meth)acrylic structural units, and polysiloxane structural units. [6] The resin composition according to any one of [1] to [5], further comprising a thermosetting resin. [7] The resin composition according to any one of [1] to [6], which is for semiconductor encapsulation. [8] The resin composition according to any one of [1] to [7], which is for use in an insulating layer of a circuit board. [9] A cured product of the resin composition according to any one of [1] to [8].

[10] A resin sheet comprising a support and a layer of the resin composition according to any one of [1] to [8] provided on the support.

[11] The resin sheet according to

[10] , wherein the support is a thermoplastic resin film or a metal foil.

[12] A semiconductor chip package comprising an encapsulating layer made of a cured product of the resin composition according to any one of [1] to [7].

[13] A circuit board comprising an insulating layer made of a cured product of the resin composition according to any one of [1] to [6] and [8].

[14] A semiconductor device comprising the semiconductor chip package according to

[12] .

[15] A semiconductor device comprising the circuit board according to

[13] . Effect of the Invention

[0008] According to the present invention, it is possible to provide a novel resin composition which has a low dielectric tangent, exhibits good elongation, and gives a cured product with excellent uniformity. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] <Terminology explanation> As used herein, the term "optionally substituted" in reference to a compound or group means both the case where the hydrogen atoms of the compound or group are not substituted with substituents, and the case where some or all of the hydrogen atoms of the compound or group are substituted with substituents.

[0010] In this specification, unless otherwise specified, the term "substituent" means a halogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an alkoxy group, a cycloalkyloxy 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 carboxy group, a sulfo group, a cyano group, a nitro group, a hydroxy group, a mercapto group, and an oxo group. In this specification, groups consisting of only carbon atoms and hydrogen atoms, such as an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an arylalkyl group, and an alkylidene group, are also referred to as a hydrocarbon group.

[0011] Examples of halogen atoms 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 in the alkyl group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3. The alkenyl group used as a substituent may be either linear or branched. The number of carbon atoms in the alkenyl group is preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 or 3. The number of carbon atoms in 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 in the alkoxy group is preferably 1 to 12, more preferably 1 to 6. The number of carbon atoms in the cycloalkyloxy 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 on the aromatic ring from an aromatic hydrocarbon. The number of carbon atoms in 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 refers to a group in which one hydrogen atom is removed from the heterocycle 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 refers to a group in which two hydrogen atoms are removed 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 even more preferably 1 to 3. The above-mentioned substituent may further have a substituent (hereinafter sometimes referred to as a "secondary substituent"). Unless otherwise specified, the same one as the above-mentioned substituent may be used as the secondary substituent.

[0012] Hereinafter, the present invention will be described in detail with reference to embodiments and examples. However, the present invention is not limited to the following embodiments and examples, and may be modified and implemented as desired without departing from the scope of the claims of the present invention and their equivalents.

[0013] [Findings of the present invention] The present inventors have discovered that by using a combination of two or more specific oligophenylene ether skeleton-containing resins, it is possible to realize a resin composition that has a low dielectric tangent, exhibits good elongation, and produces a cured product with excellent uniformity.

[0014] In detail, it was found that by using a resin composition containing an oligophenylene ether skeleton-containing resin having a molecular weight several times higher than that of a resin in combination with an oligophenylene ether skeleton-containing resin having a relatively low molecular weight, it is possible to realize a resin composition that has a low dielectric tangent, good elongation, and provides a cured product with excellent uniformity. In addition, according to the present invention, which uses a combination of two or more such oligophenylene ether skeleton-containing resins, it is possible to enjoy the benefit of further reducing the dielectric tangent by adding a high amount of inorganic filler, and to provide a cured product with good elongation and uniformity. In this way, the present invention is able to advantageously achieve a reduction in transmission loss during operation in a high-frequency environment, which is required for next-generation high-speed communication, and also contributes significantly to realizing an insulating material with good elongation and uniformity.

[0015] [Resin composition] As described above, the resin composition of the present invention is characterized by comprising, in combination with an oligophenylene ether skeleton-containing resin having a relatively low molecular weight, an oligophenylene ether skeleton-containing resin having a molecular weight several times higher than that of the aforementioned resin.

[0016] In one embodiment that is suitable from the viewpoint of providing a cured product having a low dielectric tangent, good elongation, and excellent uniformity, the resin composition of the present invention is inorganic filler, An oligophenylene ether skeleton-containing resin X having a weight average molecular weight Mw of MC, and Oligophenylene ether skeleton-containing resin Y having a weight average molecular weight Mw of MD Including, MC and MD are as follows: <Condition 1>1,000,000>MC>5MD>500 (Hereinafter, such an embodiment is also referred to as "first embodiment.") Here, resin Y corresponds to the above-mentioned "oligophenylene ether skeleton-containing resin having a relatively low molecular weight," and resin X corresponds to the above-mentioned "oligophenylene ether skeleton-containing resin having a molecular weight several times higher than that of said resin."

[0017] In addition, compared with an oligophenylene ether skeleton-containing resin (resin Y) having a relatively low molecular weight, an oligophenylene ether skeleton-containing resin having a higher molecular weight generally exhibits a low glass transition temperature (Tg). The resin X used in the present invention has a molecular weight more than 5 times higher than that of resin Y, and its glass transition temperature is usually as low as 25°C or lower. Here, the glass transition temperature of resin X being 25°C or lower means that if resin X has only one glass transition temperature, that glass transition temperature is 25°C or lower. If resin X has multiple glass transition temperatures, at least one of the glass transition temperatures is 25°C or lower. In a preferred embodiment, the resin composition of the present invention comprises: inorganic filler, An oligophenylene ether skeleton-containing resin X having a glass transition temperature of 25° C. or lower, and Resin Y containing an oligophenylene ether skeleton different from Resin X (hereinafter, such an embodiment is also referred to as "second embodiment"). Here, the glass transition temperature of resin Y is more than 25°C, preferably 60°C or higher, more preferably 80°C or higher, and even more preferably 100°C or higher, 120°C or higher, or 130°C or higher. The upper limit of the glass transition temperature of resin Y is not particularly limited, but may usually be 350°C or lower, 340°C or lower, 320°C or lower, 300°C or lower, etc.

[0018] Each component will be described below.

[0019] <Oligophenylene ether skeleton-containing resin X> Regardless of whether it is the first embodiment or the second embodiment, the resin composition of the present invention contains an oligophenylene ether skeleton-containing resin X (also simply referred to as "resin X"). By using the resin X in combination with an oligophenylene ether skeleton-containing resin Y described below, it is possible to realize a resin composition that has a low dielectric tangent, exhibits good elongation, and provides a cured product with excellent uniformity.

[0020] -Oligophenylene ether skeleton- Resin X preferably contains an oligophenylene ether skeleton containing a plurality of phenylene ether units represented by the following formula (1).

[0021] [ka] (In formula (1), R each independently represents a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aryl group, an optionally substituted amino group, a nitro group, or a carboxy group; m represents an integer of 0 to 4.

[0022] The alkyl group or alkoxy group in R may be either linear or branched, and has preferably 1 to 10 carbon atoms, more preferably 1 to 6, and further preferably 1 to 4 or 1 to 3. The number of carbon atoms does not include the number of carbon atoms of the substituent.

[0023] The number of carbon atoms in the aryl group for R is preferably 6 to 14, and more preferably 6 to 10. The number of carbon atoms does not include the number of carbon atoms of the substituent.

[0024] The substituent that the monovalent group represented by R may have is as described above, and among them, it is preferably one or more selected from a halogen atom, an alkyl group, an alkoxy group, and an aryl group, more preferably one or more selected from a halogen atom, an alkyl group, and an aryl group, and further preferably one or more selected from a fluorine atom, an alkyl group having 1 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms.

[0025] In formula (1), m represents an integer of 0 to 4, preferably an integer of 0 to 3, and more preferably an integer of 1 to 3.

[0026] In terms of providing a cured product having a low dielectric tangent, good elongation, and excellent uniformity in combination with an oligophenylene ether skeleton-containing resin Y described below, the oligophenylene ether skeleton is preferably an oligophenylene ether skeleton containing one or more units selected from the group consisting of 2,6-disubstituted-1,4-phenylene ether units, 2,5-disubstituted-1,4-phenylene ether units, and 2,3,6-trisubstituted-1,4-phenylene ether units, and particularly preferably an oligophenylene ether skeleton containing a plurality of 2,6-disubstituted-1,4-phenylene ether units (wherein the substituents at the 2,6 positions, the substituents at the 2,5 positions, and the substituents at the 2,3,6 positions correspond to R in formula (1)).

[0027] Specific examples of suitable oligophenylene ether skeletons include oligo(2,6-disubstituted-1,4-phenylene ether) skeletons such as oligo(2,6-dialkyl-1,4-phenylene ether) skeletons, oligo(2-alkyl-6-aryl-1,4-phenylene ether) skeletons, oligo(2,6-diaryl-1,4-phenylene ether) skeletons, and oligo(2,6-dihalo-1,4-phenylene ether) skeletons; 2,6-disubstituted phenols and other phenol compounds (e.g., 2,5-dialkyl phenols); and 2,3,6-trisubstituted phenols such as 2,3,6-trialkylphenol and 2,3,6-trihalophenol; and oligophenylene ether skeletons containing a plurality of 2,6-disubstituted-1,4-phenylene ether units, such as a skeleton having a copolymer structure with 2,5-disubstituted phenols such as 2,5-diphenylphenol, 2-alkyl-5-arylphenol, and 2,5-diarylphenol; and 2,3,6-trisubstituted phenols such as 2,3,6-trialkylphenol and 2,3,6-trihalophenol; and a coupling reaction product of 2,6-disubstituted phenol with a biphenol compound or a bisphenol compound.

[0028] In order to provide a cured product having a low dielectric tangent, good elongation, and excellent uniformity in combination with an oligophenylene ether skeleton-containing resin Y described below, it is preferable that the resin X contains a structure represented by the following formula (2) as the oligophenylene ether skeleton.

[0029] [ka] (In formula (2), R and m have the same meanings as above. L represents a divalent linking group. n1 and n2 each independently represent an integer of 1 to 100.

[0030] In formula (2), L represents a divalent linking group. Examples of the divalent linking group include a single bond, an alkylene group which may have a substituent, an alkenylene group which may have a substituent, an arylene group which may have a substituent, an alkylarylene group which may have a substituent, a heteroarylene group which may have a substituent, -O-, -NH-, -NR xExamples of the divalent group include -, -CO-, -CS-, -SO-, -SO2-, -C(=O)O-, -NHC(=O)-, -NC(=O)N-, -NHC(=O)O-, -C(=O)-, -S-, and divalent groups formed by combining a plurality of these. x represents a hydrocarbon group having 1 to 12 carbon atoms.

[0031] Among these, from the viewpoint of obtaining the effects of the present invention more effectively, the divalent linking group represented by L is preferably a single bond, an alkylene group which may have a substituent, an alkenylene group which may have a substituent, an arylene group which may have a substituent, -O-, -NR x Preferred are -, -CO-, -CS-, -SO-, -SO2-, and divalent groups formed by combining a plurality of these, and more preferred are a single bond, an alkylene group which may have a substituent, an arylene group which may have a substituent, and divalent groups formed by combining a plurality of these.

[0032] The substituent that the divalent group in L may have is as described above, but from the viewpoint of further enjoying the effects of the present invention, it is preferably one or more selected from a halogen atom and a hydrocarbon group, more preferably one or more selected from a halogen atom, an alkyl group, and an aryl group, and even more preferably one or more selected from a fluorine atom, an alkyl group having 1 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms.

[0033] The divalent linking group represented by L preferably has 60 or less carbon atoms, more preferably 48 or less, even more preferably 36 or less, and even more preferably 24 or less carbon atoms.

[0034] In particular, from the viewpoint of providing a cured product having a low dielectric tangent, good elongation, and excellent uniformity in combination with the oligophenylene ether skeleton-containing resin Y described below, the divalent linking group represented by L is preferably an alkylene group having 1 to 6 carbon atoms or a divalent group represented by the following formula (3):

[0035] [ka] (In formula (3), R 1 ~R 8 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group; * represents a bond.)

[0036] In formula (3), R 1 ~R 8 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. Among these, from the viewpoint of obtaining the effects of the present invention, R 1 , R 2 , R 7 and R 8 Preferably, R represents an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. 3 and R 4 Among these, it is preferable that one of them represents a hydrogen atom and the other represents an alkyl group having 1 to 6 carbon atoms, and R 5 and R 6 Of these, it is preferable that one represents a hydrogen atom and the other represents an alkyl group having 1 to 6 carbon atoms.

[0037] In formula (2), R and m are as described above for the phenylene ether unit of formula (1). Among them, the phenylene ether unit constituting the oligophenylene ether skeleton represented by formula (2) is preferably a 2,6-disubstituted-1,4-phenylene ether unit, more preferably a 2,6-dialkyl-1,4-phenylene ether unit, a 2-alkyl-6-aryl-1,4-phenylene ether unit, a 2,6-diaryl-1,4-phenylene ether unit, or a 2,6-dihalo-1,4-phenylene ether unit, from the viewpoint of being able to enjoy the effects of the present invention.

[0038] In order to provide a cured product having a lower dielectric tangent, better elongation, and more excellent uniformity in combination with an oligophenylene ether skeleton-containing resin Y described below, it is preferable that the resin X contains a structure represented by the following formula (2-1) as the oligophenylene ether skeleton.

[0039] [ka] (In formula (2-1), R, L, n1, and n2 have the same meanings as above.)

[0040] In formula (2-1), R, L, n1, and n2 have the same meanings as above, and preferred examples thereof are as described above. Among them, from the viewpoint of further enjoying the effects of the present invention, R each independently preferably represents a halogen atom, an alkyl group, or an aryl group, more preferably represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and further preferably represents an alkyl group having 1 to 6 carbon atoms; L is a single bond, an alkylene group which may have a substituent, an alkenylene group which may have a substituent, an arylene group which may have a substituent, -O-, -NR x -, -CO-, -CS-, -SO-, -SO2-, and a divalent group formed by combining a plurality of these are preferred, a single bond, an alkylene group which may have a substituent, an arylene group which may have a substituent, and a divalent group formed by combining a plurality of these are more preferred, and an alkylene group having 1 to 6 carbon atoms or a divalent group represented by the above formula (3) is even more preferred, n1 and n2 each independently represent an integer in the range of 1 to 100, and preferably represent an integer in a range such that, in relation to the flexible backbone described later, the weight average molecular weight MC of resin X satisfies the preferred conditions (the conditions are described later) including condition 1, or at least one glass transition temperature of resin X satisfies the preferred conditions (the conditions are described later).

[0041] -Flexible skeleton- Resin X contains, in addition to an oligophenylene ether skeleton, which is a rigid skeleton, a skeleton (also simply referred to as a "flexible skeleton") that is more flexible than the oligophenylene ether skeleton.

[0042] In order to provide a cured product having a lower dielectric tangent, better elongation, and more excellent uniformity in combination with an oligophenylene ether skeleton-containing resin Y described below, it is preferable that the resin X contains, as a flexible skeleton, one or more structural units selected from the group consisting of a polyolefin structural unit, a polycarbonate structural unit, a polyether structural unit, a polyester structural unit, a poly(meth)acrylic structural unit, and a polysiloxane structural unit.

[0043] Examples of polyolefin structural units include polyethylene structural units, polypropylene structural units, polybutadiene structural units, hydrogenated polybutadiene structural units, polyisopropylene structural units, hydrogenated polyisopropylene structural units, etc. Here, the term "hydrogenated polybutadiene structural units" refers to polybutadiene structural units in which some or all of the unsaturated bonds have been hydrogenated, and similarly, the term "hydrogenated polyisoprene structural units" refers to polyisoprene structural units in which some or all of the unsaturated bonds have been hydrogenated.

[0044] The polyolefin structural unit may be, for example, a structural unit remaining after removing two or more hydroxyl groups from a polyolefin structure-containing polyol compound when resin X is produced using a polyol compound having a flexible backbone as described below (in this embodiment, a polyolefin structure-containing polyol compound). The polyolefin structure-containing polyol compound may be a commercially available product, and examples of the commercially available product include "G-1000", "G-2000", and "G-3000" (polybutadiene with hydroxy groups at both ends), "GI-1000", "GI-2000", and "GI-3000" (polybutadiene with hydrogenated hydroxy groups at both ends) manufactured by Nippon Soda Co., Ltd.

[0045] Examples of the polycarbonate structural unit include aliphatic polycarbonates (polyethylene carbonate, polypropylene carbonate, polybutylene carbonate, polycyclohexane carbonate, etc.), and aromatic polycarbonates (polybisphenol A carbonate, polybisphenol F carbonate, polybisphenol S carbonate, etc.).

[0046] The polycarbonate structural unit may be, for example, a structural unit remaining after removing two or more hydroxyl groups from a polycarbonate structure-containing polyol compound when resin X is produced using a polyol compound having a flexible backbone as described below (polycarbonate structure-containing polyol compound in this embodiment). The polycarbonate structure-containing polyol compound may be a commercially available product, and examples of the commercially available product include "T6002" and "T6001" (polycarbonate with hydroxyl groups at both ends) manufactured by Asahi Kasei Chemicals Corporation, and "C-1090", "C-2015N", "C-2090", and "C-3090" (polycarbonate with hydroxyl groups at both ends) manufactured by Kuraray Co., Ltd.

[0047] Examples of the polyether structural unit include a polyethylene glycol structural unit, a polypropylene glycol structural unit, a polytetramethylene glycol structural unit, and a polybutylene glycol structural unit.

[0048] The polyether structural unit may be, for example, a structural unit remaining after removing two or more hydroxyl groups from a polyol compound having a flexible backbone as described below (a polyol compound containing a polyether structure in this embodiment) when resin X is produced using the polyol compound containing a polyether structure. The polyol compound containing a polyether structure may be a commercially available product, and examples of the commercially available product include "Pronon #102", "Pronon #104", "Pronon #201", "Pronon #202B", "Pronon #204", "Pronon #208", "Unilube 70DP-600B", and "Unilube 70DP-950B" (polyethylene glycol-polypropylene glycol copolymers) manufactured by NOF Corporation, and "Pluronic (registered trademark) L-23", "Pluronic L-31", "Pluronic L-44", "Pluronic L-61", and "ADEKA Pluronic L- 62", "Pluronic L-64", "Pluronic L-71", "Pluronic L-72", "Pluronic L-101", "Pluronic L-121", "Pluronic P-84", "Pluronic P-85", "Pluronic P-103", "Pluronic F-68", "Pluronic F-88", "Pluronic F-108", "Pluronic 25R-1", "Pluronic 25R-2", "Pluronic 17R-2", "Pluronic 17R-3", and "Pluronic 17R-4" (polyethylene glycol-polypropylene glycol copolymer).

[0049] Examples of the polyester structural unit include a polyethylene terephthalate structural unit, a polybutylene terephthalate structural unit, a polyethylene naphthalate structural unit, a polybutylene naphthalate structural unit, and a polytrimethylene terephthalate structural unit.

[0050] The polyester structural unit may be, for example, a remaining structural unit obtained by removing two or more hydroxyl groups from a polyol compound having a flexible backbone (polyester structure-containing polyol compound in this embodiment) as described later when resin X is produced. The polyester structure-containing polyol compound may be a commercially available product, and examples of the commercially available product include Vylon (registered trademark) manufactured by Toyobo Co., Ltd., Polyester (registered trademark) manufactured by Nippon Synthetic Chemical Industry Co., Ltd., and Slack (registered trademark) manufactured by Hitachi Chemical Polymer Co., Ltd.

[0051] The poly(meth)acrylic structural unit means a structural unit containing at least one of acryl and methacryl structures. For example, when resin X is produced using a polyol compound having a flexible backbone (in this embodiment, a poly(meth)acrylic structure-containing polyol compound) as described later, the poly(meth)acrylic structural unit may be a remaining structural unit obtained by removing two or more hydroxyl groups from the poly(meth)acrylic structure-containing polyol compound. The poly(meth)acrylic structure-containing polyol compound may be a commercially available product, and examples of the commercially available product include Teisan Resin "SG-600TEA" and "SG-790" (hydroxyl group-containing acrylic acid ester copolymer resin) manufactured by Nagase ChemteX Corporation, and "W-197C" (hydroxyl group-containing acrylic acid ester copolymer resin) manufactured by Negami Chemical Industries, Ltd.

[0052] Examples of the polysiloxane structural unit include a dialkylpolysiloxane structural unit, a diarylpolysiloxane structural unit, a monoalkylmonoarylpolysiloxane structural unit, and a monoalkylpolysiloxane structural unit.

[0053] The polysiloxane structural unit may be, for example, a structural unit remaining after removing two or more hydroxyl groups from a polyol compound containing a polysiloxane structure, when resin X is produced using a polyol compound having a flexible backbone as described below (a polyol compound containing a polysiloxane structure in this embodiment). The polyol compound containing a polysiloxane structure may be a commercially available product, and examples of the commercially available product include "X-21-5841" and "KF-9701" (polysiloxane with hydroxyl groups at both ends) manufactured by Shin-Etsu Chemical Co., Ltd.

[0054] As described above, the resin X includes an oligophenylene ether skeleton and a flexible skeleton. The mass ratio of the oligophenylene ether skeleton to the flexible skeleton in the resin X (flexible skeleton / oligophenylene ether skeleton) is not particularly limited as long as the weight average molecular weight MC of the resin X satisfies the preferred conditions including condition 1 (the conditions will be described later), or the glass transition temperature of the resin X satisfies the preferred conditions (the conditions will be described later). The mass ratio (flexible skeleton / oligophenylene ether skeleton) is preferably 0.2 or more, more preferably 0.4 or more, even more preferably 0.5 or more, 0.6 or more, or 0.7 or more. The condition of the mass ratio may be, for example, 3 or less, 2.5 or less, 2 or less, etc.

[0055] In the first embodiment, the weight average molecular weight MC of resin X satisfies condition 1 (i.e., more than 5 times higher than the weight average molecular weight MD of resin Y and less than 1,000,000) in relation to the weight average molecular weight MD of oligophenylene ether skeleton-containing resin Y described later. In such an embodiment, the weight average molecular weight MC of resin X is not particularly limited as long as it satisfies condition 1. In particular, in combination with oligophenylene ether skeleton-containing resin Y described later, from the viewpoint of providing a cured product with a lower dielectric tangent, better elongation, and better uniformity, the weight average molecular weight MC of resin X is preferably more than 10 times higher (MC>10MD), more preferably more than 15 times higher (MC>15MD), and even more preferably more than 20 times, more than 25 times, more than 30 times, more than 35 times, or more than 40 times higher (MC>20MD, MC>25MD, MC>30MD, MC>35MD, or MC>40MD) than the weight average molecular weight MD of resin Y.

[0056] In the first embodiment, the upper limit of the weight average molecular weight MC of resin X is less than 1,000,000, preferably less than 800,000, more preferably less than 600,000, and even more preferably less than 500,000, from the viewpoint of enjoying the effects of the present invention.

[0057] In the present invention, the weight average molecular weights MC and MD of resins X and Y are based on values ​​calculated as polystyrene, measured by gel permeation chromatography (GPC).

[0058] In the second embodiment, resin X has a glass transition temperature of 25° C. or less. If resin X has only one glass transition temperature, the glass transition temperature is 25° C. or less, and if resin X has multiple glass transition temperatures, at least one of the glass transition temperatures is 25° C. or less. If resin X has multiple glass transition temperatures, there is no particular restriction on the other glass transition temperatures as long as they have a glass transition temperature of 25° C. or less. In combination with oligophenylene ether skeleton-containing resin Y described later, from the viewpoint of providing a cured product with a lower dielectric tangent, better elongation, and more excellent uniformity, the glass transition temperature of resin X of 25° C. or less is preferably 10° C. or less, more preferably 5° C. or less, and even more preferably 0° C. or less.

[0059] In the present invention, the glass transition temperature of Resin X (and Resin Y) is based on a value measured by DSC (differential scanning calorimetry) at a heating rate of 5° C. / min.

[0060] In order to provide a cured product having a lower dielectric tangent, better elongation, and better uniformity in combination with an oligophenylene ether skeleton-containing resin Y described below, it is preferable that resin X has a weight-average molecular weight MC satisfying condition 1 and exhibits a glass transition temperature of 25° C. or lower. The suitable ranges of the weight-average molecular weight MC and the glass transition temperature are as described for the first and second embodiments, respectively.

[0061] -Synthesis of Resin X- There are no particular limitations on the synthesis procedure for resin X, so long as it is possible to achieve a structure containing the above-mentioned oligophenylene ether skeleton and flexible skeleton.

[0062] An example of the synthesis procedure for resin X is shown below.

[0063] In one embodiment, resin X is (x1) a polyol compound having a flexible skeleton; (x2) a polyisocyanate compound; (x3) an acid anhydride group-containing compound; (x4) a polyol compound containing an oligophenylene ether skeleton; It is obtained by reacting

[0064] In this reaction, the flexible skeleton of the component (x1) and the oligophenylene ether skeleton of the component (x4) are bonded via an imide structure (preferably a cyclic imide structure) formed by the reaction of the components (x2) and (x3). Thus, in one embodiment, the resin X includes an imide structure (preferably a cyclic imide structure).

[0065] As for the (x1) component, suitable examples of the flexible skeleton are as described above. As the (x1) component, any polyol compound containing a flexible skeleton may be used depending on the structure of the target resin X (i.e., the flexible skeleton), and examples of commercially available products thereof are as described above in relation to the flexible skeleton. As for the (x1) component, depending on the type of the flexible skeleton contained in the resin X, one type may be used alone, or two or more types may be used in combination.

[0066] The polyisocyanate compound of the component (x2) is not particularly limited in type, so long as it reacts with a hydroxy group and with the component (x3) to form an imide structure. Examples of the polyisocyanate compound include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; alicyclic diisocyanate compounds such as norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate; phenylene diisocyanate (p-phenylene diisocyanate, m-phenylene diisocyanate), xylylene diisocyanate (p-xylylene diisocyanate, m-xylylene diisocyanate), toluene diisocyanate, and the like. Examples of the diisocyanate include aromatic diisocyanate compounds such as toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, 3,3'-diethyldiphenyl-4,4'-diisocyanate, m-xylene diisocyanate, 1,3-bis(α,α-dimethylisocyanatomethyl)benzene, tetramethylxylylene diisocyanate, diphenylene ether-4,4'-diisocyanate, and naphthalene diisocyanate; polymethylene polyphenyl polyisocyanate; and isocyanurate-modified, biuret-modified, and allophanate-modified compounds thereof. The component (x2) may be used alone or in combination of two or more.

[0067] The type of the acid anhydride group-containing compound of the component (x3) is not particularly limited as long as it can react with the component (x2) to form an imide structure (preferably a cyclic imide structure).As the acid anhydride group-containing compound, tetracarboxylic dianhydride is preferably used, and examples thereof include pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic anhydride, p-phenylene bis(trimellitate anhydride), 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, cyclobutane tetracarboxylic anhydride, cyclopentane tetracarboxylic anhydride, 3,3'-4,4'-diphenylsulfone tetracarboxylic dianhydride, and 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3-dione. The component (x3) may be used alone or in combination of two or more.

[0068] As for the (x4) component, suitable examples of the oligophenylene ether skeleton are as described above. As the (x4) component, any polyol compound containing an oligophenylene ether skeleton may be used depending on the structure of the target resin X (i.e., the oligophenylene ether skeleton). For example, an example of a polyol compound containing an oligophenylene ether skeleton represented by the above formula (2-1) is "NORYL SA90" manufactured by Sabic. As the (x4) component, depending on the type of oligophenylene ether skeleton contained in the resin X, one type may be used alone, or two or more types may be used in combination.

[0069] The synthesis reaction of resin X using these (x1) to (x4) components may be carried out according to the conditions usually adopted in the imidization reaction using a polyol compound, an isocyanate compound, and an acid anhydride group-containing compound, and the reaction raw materials including the (x1) to (x4) components may be reacted all at once, or the (x1) to (x4) components may be reacted sequentially. When the reaction raw materials including the (x1) to (x4) components are reacted all at once, the reaction temperature may be, for example, in the range of 100 to 160°C, and the reaction time may be, for example, in the range of 4 to 10 hours. When the (x1) to (x4) components are reacted sequentially, the (x1) component and the (x2) component may be reacted, for example, in the range of 50 to 100°C for 0.5 to 4 hours, and then the (x3) component and the (x4) component may be added and reacted, for example, in the range of 120 to 160°C for 3 to 6 hours.

[0070] In the reaction of the components (x1) to (x4), a catalyst may be used, for example, tertiary amines such as tetramethylbutanediamine, benzyldimethylamine, triethanolamine, triethylamine, N,N'-dimethylpiperidine, α-methylbenzyldimethylamine, N-methylmorpholine, and triethylenediamine, and organometallic catalysts such as dibutyltin laurate, dimethyltin dichloride, cobalt naphthenate, and zinc naphthenate.

[0071] In such a reaction, by changing the degree of reaction between the (x1) component and the (x2) component or the ratio of the (x1) component to the (x4) component, it is possible to adjust the molecular weight of the resin X, the proportion of the flexible skeleton in the resin X, and ultimately the glass transition temperature of the resin X.

[0072] <Oligophenylene ether skeleton-containing resin Y> Regardless of whether it is the first embodiment or the second embodiment, the resin composition of the present invention contains an oligophenylene ether skeleton-containing resin Y (also simply referred to as "resin Y"). By using the resin Y in combination with the oligophenylene ether skeleton-containing resin X, it is possible to realize a resin composition that has a low dielectric tangent, exhibits good elongation, and provides a cured product with excellent uniformity.

[0073] Resin Y contains an oligophenylene ether skeleton, similar to resin X. Suitable examples of the oligophenylene ether skeleton contained in resin Y are as described for resin X.

[0074] That is, the resin Y preferably contains an oligophenylene ether skeleton containing a plurality of phenylene ether units represented by the above formula (1), and among these, an oligophenylene ether skeleton containing a plurality of 2,6-disubstituted-1,4-phenylene ether units is preferred. Specific preferred examples of the oligophenylene ether skeleton contained in the resin Y include oligo(2,6-dialkyl-1,4-phenylene ether) skeletons, oligo(2-alkyl-6-aryl-1,4-phenylene ether) skeletons, oligo(2,6-diaryl-1,4-phenylene ether) skeletons, oligo(2,6-dihalo-1,4-phenylene ether) skeletons, and the like; Examples of such a skeleton include a copolymer structure with a 2,5-disubstituted phenol such as a dialkylphenol, a 2-alkyl-5-arylphenol, or a 2,5-diarylphenol, or a 2,3,6-trisubstituted phenol such as a 2,3,6-trialkylphenol or a 2,3,6-trihalophenol, and an oligophenylene ether skeleton containing a plurality of 2,6-disubstituted-1,4-phenylene ether units, such as a coupling reaction product between a 2,6-disubstituted phenol and a biphenol compound or a bisphenol compound.

[0075] In combination with the above-mentioned resin X, from the viewpoint of obtaining a cured product having a low dielectric tangent, good elongation, and excellent uniformity, it is preferable that the resin Y contains a structure represented by the above formula (2) as an oligophenylene ether skeleton. In such a case, R, m, L, n1, and n2 in the formula (2) are as described above, including their preferred examples. In addition, from the viewpoint of obtaining the effects of the present invention, it is preferable that the terminals of the resin Y are each independently a hydroxyl group, a (meth)acryloyloxy group, an alkenyl group, or an alkoxysilyl group.

[0076] In terms of providing a cured product having a low dielectric tangent, good elongation and excellent uniformity in combination with the above-mentioned resin X, resin Y is preferably a compound represented by the following formula (4).

[0077] [ka] (In formula (4), R, m, L, n1, and n2 have the same meanings as above. Each X independently represents (i) a hydrogen atom, (ii) a (meth)acryloyl group, (iii) a divalent group represented by the following formula (X-1), or (iv) a monovalent hydrocarbon group substituted with a (meth)acryloyloxy group or an alkoxysilyl group.

[0078] [ka] (In formula (X-1), R has the same meaning as above, A represents an alkylene group which may have a substituent. Y represents an alkenyl group or a (meth)acryloyloxy group; m1 represents an integer of 0 to 4.

[0079] In the formula (4), R and m, including preferred examples thereof, are as described above for the phenylene ether unit in the formula (1).

[0080] In the formula (4), L, including preferred examples thereof, is as described above for the oligophenylene ether skeleton of the formula (2).

[0081] In formula (4), n1 and n2 each independently represent an integer in the range of 1 to 100, and preferably represent an integer in such a range that the weight average molecular weight MD of resin Y satisfies condition 1 and other suitable conditions.

[0082] In formula (4), X's each independently represent (i) a hydrogen atom, (ii) a (meth)acryloyl group, (iii) a divalent group represented by formula (X-1) above, or (iv) a hydrocarbon group substituted with a (meth)acryloyloxy group or an alkoxysilyl group. Here, the term "(meth)acryloyl group" encompasses both a methacryloyl group and an acryloyl group, and the term "(meth)acryloyloxy group" encompasses both a methacryloyloxy group and an acryloyloxy group.

[0083] The case where X represents a divalent group represented by the above formula (X-1), that is, the above embodiment (iii), will be described below.

[0084] In formula (X-1), R, including preferred examples thereof, is as described above for the phenylene ether unit of formula (1).

[0085] In formula (X-1), A represents an alkylene group which may have a substituent. The alkylene group in A may be either linear or branched, and the number of carbon atoms is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3. The substituent which the alkylene group may have is as described above, and among them, from the viewpoint of further enjoying the effects of the present invention, one or more types selected from a halogen atom and a hydrocarbon group are preferable, one or more types selected from a halogen atom, an alkyl group, and an aryl group are more preferable, and one or more types selected from a fluorine atom, an alkyl group having 1 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms are even more preferable.

[0086] In formula (X-1), Y represents an alkenyl group or a (meth)acryloyloxy group. The alkenyl group represented by Y may be either linear or branched, and has preferably 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, and further preferably 2 or 3 carbon atoms. In terms of being able to further enjoy the effects of the present invention in combination with resin X, the alkenyl group represented by Y is preferably a vinyl group or an allyl group.

[0087] In formula (X-1), m1 represents an integer of 0 to 4, preferably 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0088] The case where X represents a hydrocarbon group substituted with a (meth)acryloyloxy group or an alkoxysilyl group, that is, the above embodiment (iv), will be described below.

[0089] Regardless of whether X represents a hydrocarbon group substituted with a (meth)acryloyloxy group or an alkoxysilyl group, the hydrocarbon group in X is a hydrocarbon group having one or more (preferably 1 to 50, more preferably 1 to 20) carbon atoms as skeletal atoms and hydrogen atoms as non-skeletal atoms. The hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. The hydrocarbon group may or may not have an aromatic structure. Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an aryl group, an arylalkyl group (aralkyl group), an alkylaryl group, an alkylaralkyl group, an alkenylaryl group, an alkenylaralkyl group, an alkenylalkylaryl group, and an alkenylalkylaralkyl group. Here, the number of carbon atoms in the alkyl group is preferably 1 to 14, more preferably 1 to 6, the number of carbon atoms in the alkenyl group is preferably 2 to 14, more preferably 2 to 6, the number of carbon atoms in the aryl group is preferably 6 to 14, more preferably 6 to 10, the number of carbon atoms in the aralkyl group and the arylalkyl group is preferably 7 to 15, more preferably 7 to 11, the number of carbon atoms in the alkylaralkyl group is preferably 8 to 16, more preferably 8 to 12, the number of carbon atoms in the alkenylaryl group is preferably 8 to 15, more preferably 8 to 11, the number of carbon atoms in the alkenylaralkyl group and the alkenylalkylaryl group is preferably 9 to 16, more preferably 9 to 12, and the number of carbon atoms in the alkenylalkylaralkyl group is preferably 10 to 17, more preferably 10 to 13. When one or more hydrogen atoms of these hydrocarbon groups are It is substituted with a meth)acryloyloxy group or an alkoxysilyl group.

[0090] When X represents a hydrocarbon group substituted with an alkoxysilyl group, examples of the alkoxysilyl group include a trialkoxysilyl group, a dialkoxymonoalkylsilyl group, and a monoalkoxydialkylsilyl group. The number of carbon atoms of the alkoxy group in the alkoxysilyl group is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 or 2, and the number of carbon atoms of the alkyl group (if included) in the alkoxysilyl group is preferably 1 to 14, more preferably 1 to 10, and even more preferably 1 to 6.

[0091] In the first embodiment, the weight average molecular weight MD of resin Y satisfies condition 1 (i.e., more than 100 and less than 1 / 5 of the weight average molecular weight MC of resin X) in relation to the weight average molecular weight MC of resin X described above. In this embodiment, the weight average molecular weight MD of resin Y is not particularly limited as long as it satisfies condition 1. In particular, in terms of providing a cured product with a lower dielectric tangent, better elongation, and better uniformity in combination with the above-mentioned resin X, the lower limit of the weight average molecular weight MD of resin Y is more than 100, preferably more than 500, more preferably more than 1000, and even more preferably more than 1500 or more than 2000. The suitable range of the upper limit of the weight average molecular weight MD of resin Y is as described above in relation to the weight average molecular weight MC of resin X.

[0092] In the second embodiment, the glass transition temperature of the resin Y is higher than 25° C., and the suitable range thereof is as described above.

[0093] From the viewpoint of providing a cured product with a lower dielectric tangent, better elongation, and more excellent uniformity in combination with resin X, resin Y preferably has a weight-average molecular weight MD satisfying condition 1 and exhibits a glass transition temperature of more than 25° C. The preferred ranges of the weight-average molecular weight MD and the glass transition temperature are as described in the first and second embodiments, respectively.

[0094] Resin Y may be a commercially available product, for example, "NORYL SA9000" manufactured by Sabic (in formula (4), R is a methyl group, m is 2, L is a C3 alkylene group, X is a methacryloyl group, n1 and n2 are values ​​that result in a weight average molecular weight of about 3900; contains an oligo(2,6-dialkyl-1,4-phenylene ether) skeleton), "NORYL SA90 (in formula (4), R is a methyl group, m is 2, L is a C3 alkylene group, X is a hydrogen atom, n1 and n2 are values ​​that result in a weight-average molecular weight of about 4,400; contains an oligo(2,6-dialkyl-1,4-phenylene ether) skeleton), manufactured by Mitsubishi Gas Chemical Company, Inc. (in formula (4), R is a methyl group, m is 2, L is a divalent group represented by formula (3), X is a group represented by formula (X-1) [m1 is 0, A is a C1 alkylene group, Y is a C2 alkenyl group], n1 and n2 are values ​​that result in a weight-average molecular weight of about 3000; containing an oligo(2,6-dialkyl-1,4-phenylene ether) skeleton), and "X-12-1288C" and "X-12-1288D" manufactured by Shin-Etsu Chemical Co., Ltd. ((in formula (4), R is a methyl group, m is 2, X is a hydrocarbon group substituted with a methacryloyloxy group or a trialkoxysilyl group, n1 and n2 are values ​​such that the weight average molecular weight is about 3500 to 3600; containing an oligo(2,6-dialkyl-1,4-phenylene ether) skeleton).

[0095] From the viewpoint of obtaining a cured product having a low dielectric tangent, good elongation, and excellent uniformity, when the resin components in the resin composition are taken as 100% by mass, the total content of resin X and resin Y in the resin composition is preferably 20% by mass or more, more preferably 25% by mass or more, even more preferably 30% by mass or more, 32% by mass or more, 34% by mass or more, or 35% by mass or more. From the same viewpoint, the upper limit of the total content is preferably less than 70% by mass, more preferably 65% ​​by mass or less, even more preferably 60% by mass or less, 58% by mass or less, 56% by mass or less, or 55% by mass or less. Therefore, in one embodiment, when the resin components in the resin composition are taken as 100% by mass, the total content of resin X and resin Y is 20% by mass or more and less than 70% by mass.

[0096] In the present invention, the "resin component" of the resin composition refers to the non-volatile components constituting the resin composition excluding the inorganic filler described below.

[0097] From the viewpoint of obtaining a cured product having a lower dielectric tangent, better elongation, and better uniformity, the mass ratio of resin X to resin Y (resin X / resin Y) is preferably 0.3 or more, more preferably 0.6 or more, 0.8 or more, or 1 or more, more preferably more than 1, 1.2 or more, 1.4 or more, 1.5 or more, 1.6 or more, 1.8 or more, or 2 or more, and even more preferably 2.2 or more, 2.4 or more, or 2.5 or more. In particular, when the mass ratio of resin X / resin Y is more than 1, it is preferable because it is easy to obtain a cured product having excellent dielectric tangent, elongation, and uniformity. From the same viewpoint, the upper limit of the mass ratio is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less, 9.5 or less, or 9 or less.

[0098] The content of resin X in the resin composition is not particularly limited as long as the above-mentioned preferred ranges of the total content and mass ratio are satisfied in relation to the content of resin Y, but when the resin component in the resin composition is taken as 100 mass%, the content is preferably 5 mass% or more, more preferably 10 mass% or more, even more preferably 15 mass% or more, still more preferably 20 mass% or more, 22 mass% or more, 24 mass% or more, or 25 mass% or more, and the upper limit is preferably 66 mass% or less, more preferably 60 mass% or less, even more preferably 55 mass% or less, 50 mass% or less, 48 ​​mass% or less, 46 mass% or less, or 45 mass% or less.

[0099] <Inorganic filler> The resin composition of the present invention contains an inorganic filler regardless of whether it is the first embodiment or the second embodiment. By containing an inorganic filler, the dielectric loss tangent can be reduced.

[0100] Examples of inorganic fillers include 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. Among these, silica is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. In addition, spherical silica is preferred as the silica. The inorganic filler may be used alone or in combination of two or more.

[0101] Examples of commercially available inorganic fillers include "SP60-05" and "SP507-05" manufactured by Nippon Steel Chemical & Material 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.; "Silfil NSS-3N", "Silfil NSS-4N", and "Silfil NSS-5N" manufactured by Tokuyama Corporation; "Cellspheres" and "MGH-005" manufactured by Pacific Cement Corporation; and "Sferique" and "BA-1" manufactured by JGC Catalysts and Chemicals Co., Ltd.

[0102] The average particle size of the inorganic filler is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, even 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 size is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, even more preferably 0.07 μm or more, 0.1 μm or more, or 0.2 μm or more. The average particle size of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is created on a volume basis using a laser diffraction / scattering particle size distribution measuring device, and the median diameter is used as the average particle size. The measurement sample can be prepared by weighing 100 mg of the inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing it by ultrasonic waves for 10 minutes. The measurement sample is measured using a laser diffraction particle size distribution measuring device with blue and red light source wavelengths used, and the volume-based particle size distribution of the inorganic filler is measured using a flow cell method, and the average particle size is calculated as the median diameter from the particle size distribution obtained. An example of a laser diffraction particle size distribution measuring device is the "LA-960" manufactured by Horiba, Ltd.

[0103] The specific surface area of ​​the inorganic filler is not particularly limited, but is preferably 0.1 m 2 / g or more, more preferably 0.5m 2 / g or more, more preferably 1m 2 / g or more, 3m 2 / g or more or 5m 2 The upper limit of the specific surface area is not particularly limited, but is preferably 100 m 2 / g or less, more preferably 80m 2 / g or less, more preferably 60m 2 / g or less, 50m 2 / g or less or 40m 2 / g or less. The specific surface area of ​​the inorganic filler is obtained according to the BET method by adsorbing nitrogen gas onto the surface of the sample using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountec Co., Ltd.) and calculating the specific surface area using the BET multipoint method.

[0104] The inorganic filler is preferably surface-treated with a suitable surface treatment agent. By performing the surface treatment, the moisture resistance and dispersibility of the inorganic filler can be improved. Examples of the surface treatment agent include silane coupling agents such as 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, and acid anhydride silane coupling agents; non-silane coupling-alkoxysilane compounds such as methyltrimethoxysilane and phenyltrimethoxysilane; and silazane compounds. The surface treatment agent may be used alone or in combination of two or more.

[0105] Examples of commercially available surface treatment agents include Shin-Etsu Chemical Co., Ltd.'s "KBM403" (3-glycidoxypropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM803" (3-mercaptopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), and Shin-Etsu Chemical Co., Ltd.'s "SZ-31" (hexamethyldisilazane).

[0106] The degree of surface treatment with the surface treatment agent is preferably within a predetermined range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, it is preferable that 100% by mass of the inorganic filler is surface-treated with 0.2 to 5% by mass of the surface treatment agent.

[0107] The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of ​​the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of ​​the inorganic filler is set to 0.02 mg / m 2 More than 0.1 mg / m is preferable. 2 More preferably, 0.2 mg / m or more 2On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin composition or the melt viscosity in the form of a sheet, it is more preferable that the melt viscosity is 1.0 mg / m 2 Less than 0.8 mg / m is preferred. 2 Less than 0.5 mg / m is more preferable. 2 The following is more preferable. The amount of carbon per unit surface area of ​​the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler that has been surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of ​​the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, an "EMIA-320V" manufactured by Horiba, Ltd., or the like can be used.

[0108] In the combination with resins X and Y, from the viewpoint of providing a cured product with low dielectric tangent, good elongation, and excellent uniformity, the content of the inorganic filler in the resin composition is preferably 50% by mass or more, more preferably 55% by mass, and even more preferably 60% by mass or more, when the non-volatile components in the resin composition are taken as 100% by mass. As described above, in a system containing resin Y, when the inorganic filler is highly blended to achieve a low dielectric tangent, the cured product tends to have poor elongation and uniformity. In contrast, according to the present invention in which resin X is used in combination with resin Y, the content of the inorganic filler can be further increased while suppressing deterioration of elongation and uniformity. For example, the content of the inorganic filler in the resin composition may be increased to 62% by mass or more, 64% by mass or more, 65% by mass or more, 66% by mass or more, or 68% by mass or more, when the non-volatile components in the resin composition are taken as 100% by mass. The upper limit of the content of the inorganic filler is not particularly limited, but may be, for example, 90% by mass or less, 85% by mass or less, etc.

[0109] <Thermosetting resin> The resin composition of the present invention may further contain a thermosetting resin.

[0110] The thermosetting resin is not particularly limited, but examples thereof include epoxy resin, benzocyclobutene resin, epoxy acrylate resin, urethane acrylate resin, urethane resin, cyanate resin, polyimide resin, benzoxazine resin, unsaturated polyester resin, melamine resin, silicone resin, etc. Among them, it is preferable to include an epoxy resin in combination with resins X and Y, from the viewpoint of providing a cured product having a low dielectric tangent, good elongation, and excellent uniformity.

[0111] The type of epoxy resin is not particularly limited as long as it has one or more (preferably two or more) epoxy groups in one molecule. Examples of epoxy resins include bisphenol type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol novolac type epoxy resins, phenol novolac 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 novolac type epoxy resins, biphenyl type epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, cyclohexane type epoxy resins, cyclohexane dimethanol type epoxy resins, naphthylene ether type epoxy resins, trimethylol type epoxy resins, and tetraphenylethane type epoxy resins. Bisphenol type epoxy resin refers to an epoxy resin having a bisphenol structure, such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and bisphenol AF type epoxy resin. Biphenyl type epoxy resin refers to an epoxy resin having a biphenyl structure, where the biphenyl structure may have a substituent such as an alkyl group, an alkoxy group, or an aryl group. Therefore, bixylenol type epoxy resin and biphenyl aralkyl type epoxy resin are also included in biphenyl type epoxy resin.

[0112] Epoxy resins can be classified into epoxy resins that are liquid at a temperature of 20°C (hereinafter referred to as "liquid epoxy resins") and epoxy resins that are solid at a temperature of 20°C (hereinafter referred to as "solid epoxy resins"). 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.

[0113] The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule.

[0114] As the liquid epoxy resin, glycirol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane dimethanol type epoxy resin, cyclic aliphatic glycidyl ether, and epoxy resin having a butadiene structure are preferred.

[0115] Specific examples of liquid epoxy resins include "EX-992L" manufactured by Nagase ChemteX Corporation, "YX7400" manufactured by Mitsubishi Chemical Corporation, "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resins) manufactured by DIC Corporation; "828US", "828EL", and "825" (bisphenol A type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "jER807" and "1750" (bisphenol F type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac type epoxy resin) manufactured by Ryo Chemical; "630", "630LSD", and "604" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical; "ED-523T" (glycirol type epoxy resin) manufactured by ADEKA; "EP-3950L" and "EP-3980S" (glycidylamine type epoxy resin) manufactured by ADEKA; "EP-4088S" (dicyclopentadiene type epoxy resin) manufactured by ADEKA ); "ZX1059" manufactured by Nippon Steel Chemical & Material Co., Ltd. (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); "EX-721" manufactured by Nagase ChemteX Corporation (glycidyl ester type epoxy resin); "EX-991L" manufactured by Nagase ChemteX Corporation (an epoxy resin containing an alkyleneoxy skeleton and a butadiene skeleton); "Celloxide 2021P" manufactured by Daicel Corporation (an alicyclic epoxy resin having an ester skeleton); "PB-3600" manufactured by Daicel Corporation, "JP-100" and "JP-200" manufactured by Nippon Soda Co., Ltd. (an epoxy resin having a butadiene structure); "ZX1658" and "ZX1658GS" manufactured by Nippon Steel Chemical & Material Co., Ltd. (liquid 1,4-glycidylcyclohexane type epoxy resin); "EG-280" manufactured by Osaka Gas Chemical Co., Ltd. (an epoxy resin containing a fluorene structure); and "EX-201" manufactured by Nagase ChemteX Corporation (cyclic aliphatic glycidyl ether).

[0116] As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferable, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferable.

[0117] Preferred solid epoxy resins include bixylenol type epoxy resins, naphthalene type epoxy resins, naphthalene type tetrafunctional epoxy resins, naphthol novolac type epoxy resins, cresol novolac type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol type epoxy resins, biphenyl type epoxy resins, naphthylene ether type epoxy resins, anthracene type epoxy resins, bisphenol A type epoxy resins, bisphenol AF type epoxy resins, phenol aralkyl type epoxy resins, tetraphenylethane type epoxy resins, and phenolphthalimidine type epoxy resins.

[0118] Specific examples of solid epoxy resins include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC Corporation; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resins) manufactured by DIC Corporation; "N-690" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "HP-7200", "HP-7200HH", "HP-7200H", and "HP-7200L" (dicyclopentadiene type epoxy resins) manufactured by DIC Corporation; "EXA-7311" and "E XA-7311-G3, EXA-7311-G4, EXA-7311-G4S, HP-6000, HP-6000L (naphthylene ether type epoxy resin); Nippon Kayaku's "EPPN-502H" (trisphenol type epoxy resin); Nippon Kayaku's "NC7000L" (naphthol novolac type epoxy resin); Nippon Kayaku's "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin); Nippon Steel Chemical & Material's "ESN475V" , "ESN4100V" (naphthalene type epoxy resin); "ESN485" (naphthol type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "ESN375" (dihydroxynaphthalene type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YX4000H", "YX4000", "YX4000HK", "YL7890" (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. Examples of epoxy resins that can be used include "YX7700" (phenol aralkyl type epoxy resin) manufactured by Osaka Gas Chemicals; "PG-100" and "CG-500" manufactured by Osaka Gas Chemicals; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1010" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation; and "WHR991S" (phenolphthalimidine type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.These may be used alone or in combination of two or more.

[0119] When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, the mass ratio thereof (liquid epoxy resin:solid epoxy resin) is preferably 10:1 to 1:50, more preferably 5:1 to 1:20, even more preferably 2:1 to 1:10, and particularly preferably 1:1 to 1:3.

[0120] The epoxy equivalent of the epoxy resin is preferably 50 g / eq. to 5,000 g / eq., more preferably 60 g / eq. to 2,000 g / eq., even more preferably 70 g / eq. to 1,000 g / eq., and even more preferably 80 g / eq. to 500 g / eq. The epoxy equivalent is the mass of the resin per equivalent of epoxy group. This epoxy equivalent can be measured according to JIS K7236.

[0121] The weight average molecular weight of the epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, and further preferably 400 to 1500. The weight average molecular weight of the resin can be measured by gel permeation chromatography (GPC) as a polystyrene-equivalent value.

[0122] When the resin composition of the present invention contains a thermosetting resin, the content of the thermosetting resin in the resin composition is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 12% by mass or more, 14% by mass or more, or 15% by mass or more, when the resin component in the resin composition is 100% by mass. The upper limit of the content is not particularly limited and may be determined depending on the properties required for the resin composition, but may be, for example, 60% by mass or less, 50% by mass or less, or 40% by mass or less.

[0123] <Hardening agent> The resin composition of the present invention may further contain a curing agent.

[0124] The curing agent is not particularly limited, but examples thereof include active ester curing agents, phenol curing agents, naphthol curing agents, carbodiimide curing agents, acid anhydride curing agents, amine curing agents, benzoxazine curing agents, cyanate ester curing agents, and thiol curing agents. The curing agent may be used alone or in combination of two or more. From the viewpoint of being able to enjoy the effects of the present invention, it is preferable that the curing agent is one or more selected from active ester curing agents, phenol curing agents, and carbodiimide curing agents.

[0125] As the active ester curing agent, a compound having one or more active ester groups in one molecule can be used. Among them, as the active ester curing agent, a compound having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, is preferable. The active ester curing agent is preferably one obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent derived from a carboxylic acid compound is preferable, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is more preferable, and an active ester curing agent obtained from a carboxylic acid compound and an aromatic hydroxy compound is even more preferable.

[0126] The carboxylic acid compound may be either an aromatic carboxylic acid compound or an aliphatic carboxylic acid compound, and examples thereof include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and halides thereof.

[0127] Examples of aromatic hydroxy compounds include (i) polyaddition products of unsaturated aliphatic cyclic compounds containing two double bonds in one molecule and phenols, (ii) various bisphenol compounds, (iii) aromatic polyols having two or more hydroxyl groups bonded to the carbon atoms on the aromatic ring, and (iv) aromatic monools having one hydroxyl group bonded to the carbon atoms on the aromatic ring. Examples of polyaddition products of unsaturated aliphatic cyclic compounds and phenols include polyaddition products of unsaturated aliphatic cyclic compounds such as dicyclopentadiene, tetrahydroindene, norbornadiene, limonene, and vinylcyclohexene with phenols that may have a substituent (e.g., phenol, cresol, xylenol, ethylphenol, propylphenol, vinylphenol, allylphenol, phenylphenol, benzylphenol, halophenol, etc.), and specifically, for example, dicyclopentadiene-phenols polyaddition products. Examples of bisphenol compounds include bisphenol A, bisphenol F, bisphenol AF, bisphenol AP, bisphenol B, bisphenol BP, bisphenol C, and bisphenol M. Examples of aromatic polyols having two or more hydroxy groups bonded to carbon atoms on an aromatic ring include hydroquinone, resorcinol, catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, and phenol novolak. Examples of aromatic monools having one hydroxy group bonded to a carbon atom on an aromatic ring include phenol, cresol, xylenol, ethylphenol, propylphenol, vinylphenol, allylphenol, phenylphenol, benzylphenol, halophenol, naphthol, methylnaphthol, dimethylnaphthol, ethylnaphthol, propylnaphthol, vinylnaphthol, allylnaphthol, phenylnaphthol, benzylnaphthol, and halonaphthol.

[0128] Suitable specific examples of the active ester curing agent include an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and an active ester compound containing a benzoylated product of phenol novolac. Among them, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene-type diphenol structure are more preferred. The "dicyclopentadiene-type diphenol structure" refers to a divalent structural unit consisting of phenylene-dicyclopentalene-phenylene.

[0129] Commercially available active ester curing agents include active ester compounds containing a dicyclopentadiene-type diphenol structure, such as "EXB9451", "EXB9460", "EXB9460S", "HPC-8000L-65TM", "HPC-8000-65T", "HPC-8000H", and "HPC-8000H-65TM" (manufactured by DIC Corporation); and active ester compounds containing a naphthalene structure, such as "HP-B-8151-62T", "EXB-8100L-65T", "EXB-9416-70BK", and "HPC-8150-62T". and "EXB-8" (manufactured by DIC Corporation); an active ester compound containing phosphorus, "EXB9401" (manufactured by DIC Corporation), an active ester compound which is an acetylated product of phenol novolac, "DC808" (manufactured by Mitsubishi Chemical Corporation), active ester compounds which are benzoylated products of phenol novolac, "YLH1026", "YLH1030", and "YLH1048" (manufactured by Mitsubishi Chemical Corporation), and an active ester compound containing a styryl group and a naphthalene structure, "PC1300-02-65MA" (manufactured by Air Water Corporation), etc.

[0130] As the phenol-based curing agent and naphthol-based curing agent, from the viewpoint of heat resistance and water resistance, a phenol-based curing agent having a novolac structure or a naphthol-based curing agent having a novolac structure is preferred. Also, from the viewpoint of achieving an insulating layer having good adhesion strength (peel strength) with a conductor layer, a nitrogen-containing phenol-based curing agent or a nitrogen-containing naphthol-based curing agent is preferred, and a triazine skeleton-containing phenol-based curing agent or a triazine skeleton-containing naphthol-based curing agent is more preferred. Among them, from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion strength with a conductor layer, a triazine skeleton-containing phenol novolac resin or a triazine skeleton-containing naphthol novolac resin is preferred.

[0131] Specific examples of phenol-based curing agents and naphthol-based curing agents include, for example, "MEH-7700", "MEH-7810", "MEH-7851", and "MEH-8000H" manufactured by Meiwa Chemical Industry Co., Ltd.; "NHN", "CBN", and "GPH" manufactured by Nippon Kayaku Co., Ltd.; and "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-495V", and "SN-37" manufactured by Nippon Steel Chemical & Material Co., Ltd. 5" and "SN-395" manufactured by DIC Corporation; "TD-2090", "TD-2090-60M", "LA-7052", "LA-7054", "LA-1356", "LA-3018", "LA-3018-50P", "EXB-9500", "HPC-9500", "KA-1160", "KA-1163", and "KA-1165" manufactured by Gun-ei Chemical Co., Ltd.; and the like.

[0132] Examples of the carbodiimide-based curing agent include curing agents having one or more, preferably two or more, carbodiimide structures in one molecule, such as aliphatic biscarbodiimides, such as tetramethylene-bis(t-butylcarbodiimide) and cyclohexane bis(methylene-t-butylcarbodiimide); aromatic biscarbodiimides, such as phenylene-bis(xylylcarbodiimide); and aliphatic polycarbodiimides, such as polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylenecarbodiimide, poly(methylenebiscyclohexylenecarbodiimide), and poly(isophoronecarbodiimide). ; polycarbodiimides such as aromatic polycarbodiimides such as poly(phenylenecarbodiimide), poly(naphthylenecarbodiimide), poly(tolylenecarbodiimide), poly(methyldiisopropylphenylenecarbodiimide), poly(triethylphenylenecarbodiimide), poly(diethylphenylenecarbodiimide), poly(triisopropylphenylenecarbodiimide), poly(diisopropylphenylenecarbodiimide), poly(xylylenecarbodiimide), poly(tetramethylxylylenecarbodiimide), poly(methylenediphenylenecarbodiimide), and poly[methylenebis(methylphenylene)carbodiimide].

[0133] Commercially available carbodiimide curing agents include, for example, "Carbodilite V-02B", "Carbodilite V-03", "Carbodilite V-04K", "Carbodilite V-07", and "Carbodilite V-09" manufactured by Nisshinbo Chemical Inc.; and "Stavaxol P", "Stavaxol P400", and "Hi-Kasil 510" manufactured by Rhein Chemie.

[0134] Examples of the acid anhydride curing agent include a curing agent having one or more acid anhydride groups in one molecule, and a curing agent having two or more acid anhydride groups in one molecule is preferable. Specific examples of the acid anhydride curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, and the like. Examples of acid anhydrides include anhydrides, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis(anhydrotrimellitate), and polymeric acid anhydrides such as styrene-maleic acid resin, which is a copolymer of styrene and maleic acid. Commercially available acid anhydride curing agents include "HNA-100", "MH-700", "MTA-15", "DDSA", and "OSA" manufactured by New Japan Chemical Co., Ltd., "YH-306" and "YH-307" manufactured by Mitsubishi Chemical Corporation, "HN-2200" and "HN-5500" manufactured by Hitachi Chemical Co., Ltd., and "EF-30", "EF-40", "EF-60", and "EF-80" manufactured by Clay Valley.

[0135] The amine-based curing agent may be a curing agent having one or more, preferably two or more, amino groups in one molecule, such as aliphatic amines, polyether amines, alicyclic amines, aromatic amines, etc., and among them, aromatic amines are preferred from the viewpoint of achieving the desired effects of the present invention. The amine-based curing agent is preferably a primary amine or secondary amine, and more preferably a primary amine. Specific examples of amine-based curing agents include 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, and 2,2-bis(3-amino-4-hydroxyphenyl)propane. 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, and the like. As the amine-based curing agent, commercially available products may be used, and examples thereof include "SEIKACURE-S" manufactured by Seika Corporation, "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD AA", "KAYAHARD AB", and "KAYAHARD AS" manufactured by Nippon Kayaku Co., Ltd., and "Epicure W" manufactured by Mitsubishi Chemical Corporation.

[0136] Specific examples of benzoxazine-based curing agents include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Corporation; "HFB2006M" manufactured by Showa Polymer Co., Ltd.; and "Pd" and "Fa" manufactured by Shikoku Chemical Industry Co., Ltd.

[0137] Examples of the cyanate ester curing agent include bifunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanate phenyl-1-(methylethylidene))benzene, bis(4-cyanate phenyl)thioether, and bis(4-cyanate phenyl)ether; polyfunctional cyanate resins derived from phenol novolac and cresol novolac; and prepolymers in which these cyanate resins are partially converted to triazine. Specific examples of cyanate ester-based curing agents include "PT30" and "PT60" (both of which are phenol novolac-type multifunctional cyanate ester resins), "BA230" and "BA230S75" (prepolymers in which part or all of bisphenol A dicyanate has been converted to triazine to form a trimer), all of which are manufactured by Lonza Japan.

[0138] Examples of thiol-based curing agents include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), and tris(3-mercaptopropyl)isocyanurate.

[0139] The reactive group equivalent of the curing agent is preferably 50 g / eq. to 3000 g / eq., more preferably 100 g / eq. to 1000 g / eq., further preferably 100 g / eq. to 500 g / eq., and particularly preferably 100 g / eq. to 300 g / eq. The reactive group equivalent is the mass of the curing agent per equivalent of the reactive group.

[0140] From the viewpoint of producing a cured product with a low dielectric tangent, the curing agent preferably contains an active ester curing agent. When the curing agent contains an active ester curing agent, the content of the active ester curing agent is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more or 60% by mass or more, when the non-volatile components in the curing agent are taken as 100% by mass, and the upper limit may be 100% by mass, but may also be, for example, 98% by mass or less, 95% by mass or less, or 90% by mass or less.

[0141] When the resin composition of the present invention contains a curing agent, the content of the curing agent in the resin composition is not particularly limited, but is preferably 3% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, 15% by mass or more, or 20% by mass or more, when the resin component in the resin composition is 100% by mass. The upper limit of the content of the curing agent is preferably 60% by mass or less, more preferably 50% by mass or less, 45% by mass or less, 40% by mass or less, or 35% by mass or less.

[0142] <Curing accelerator> The resin composition of the present invention may further contain a curing accelerator. By containing a curing accelerator, the curing time and the curing temperature can be efficiently adjusted.

[0143] Examples of the curing accelerator include phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, and amine-based curing accelerators. From the viewpoint of obtaining the effects of the present invention, it is preferable that the curing accelerator contains an amine-based curing accelerator or an imidazole-based curing accelerator. The curing accelerator may be used alone or in combination of two or more.

[0144] Examples of the phosphorus-based curing accelerator include aliphatic phosphonium salts such as tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium)pyromellitate, tetrabutylphosphonium hydrogenhexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, and di-tert-butylmethylphosphonium tetraphenylborate; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate ... aromatic phosphonium salts such as tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane; aromatic phosphine-quinone adducts such as triphenylphosphine-p-benzoquinone adduct; aliphatic phosphines such as tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl(2-butenyl)phosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, and tricyclohexylphosphine;Dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-isopropylphenyl)phosphine, tris(4-butylphenyl)phosphine, tris(4-tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,5-dimethylphenyl)phosphine, tris(2,6-dimethylphenyl)phosphine Examples of aromatic phosphines include tris(3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, and 2,2'-bis(diphenylphosphino)diphenyl ether.

[0145] Examples of the urea-based curing accelerator include 1,1-dimethylurea; aliphatic dimethylureas such as 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, and 3-cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, and 3-(3,4-dimethylphenyl)-1,1-dimethylurea. aromatic dimethylureas such as butylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N',N'-dimethylurea), and N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluene bisdimethylurea].

[0146] Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, and 1-(o-tolyl)biguanide.

[0147] Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, and 1-benzyl-2-methylimidazole. Phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl -(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct imidazole compounds such as 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, as well as adducts of imidazole compounds and epoxy resins.

[0148] As the imidazole-based curing accelerator, commercially available products may be used, for example, "1B2PZ", "2E4MZ", "2MZA-PW", "2MZ-OK", "2MA-OK", "2MA-OK-PW", "2P4MZ", "2PHZ", "2PHZ-PW", "Cl1Z", "Cl1Z-CN", "Cl1Z-CNS", and "C11Z-A" manufactured by Shikoku Chemical Industry Co., Ltd.; "P200-H50" manufactured by Mitsubishi Chemical Corporation, etc. These may be used alone or in combination of two or more kinds.

[0149] Examples of metal-based curing accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organocobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate, organocopper complexes such as copper(II) acetylacetonate, organozinc complexes such as zinc(II) acetylacetonate, organoiron complexes such as iron(III) acetylacetonate, organonickel complexes such as nickel(II) acetylacetonate, and organomanganese complexes such as manganese(II) acetylacetonate. Examples of organometallic salts include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0150] Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine (DMAP), benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc. Commercially available amine-based curing accelerators may be used, such as "MY-25" manufactured by Ajinomoto Fine-Techno Co., Ltd.

[0151] When the resin composition of the present invention contains a curing accelerator, the content of the curing accelerator in the resin composition is not particularly limited, but when the resin component in the resin composition is taken as 100 mass%, it is preferably 0.01 mass% or more, more preferably 0.03 mass% or more, and even more preferably 0.05 mass% or more, and the upper limit is preferably 3 mass% or less, more preferably 2 mass% or less, 1.5 mass% or less, or 1 mass% or less.

[0152] <Radical polymerization initiator> The resin composition of the present invention may further contain a radical polymerization initiator. The radical polymerization initiator may be used alone or in combination of two or more kinds.

[0153] Examples of the radical polymerization initiator include peroxide radical polymerization initiators, azo radical polymerization initiators, etc. Among them, peroxide radical polymerization initiators are preferred.

[0154] Examples of the peroxide radical polymerization initiator include hydroperoxide compounds such as 1,1,3,3-tetramethylbutyl hydroperoxide; dialkyl peroxide compounds such as tert-butylcumyl peroxide, di-tert-butyl peroxide, di-tert-hexyl peroxide, dicumyl peroxide, 1,4-bis(1-tert-butylperoxy-1-methylethyl)benzene, and 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane; and diacyl peroxide compounds such as dilauroyl peroxide, didecanoyl peroxide, dicyclohexyl peroxydicarbonate, and bis(4-tert-butylcyclohexyl)peroxydicarbonate. peroxyester compounds such as tert-butyl peroxyacetate, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl monocarbonate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyneodecanoate, tert-hexylperoxyisopropyl monocarbonate, tert-butyl peroxylaurate, (1,1-dimethylpropyl)2-ethylperhexanoate, tert-butyl 2-ethylperhexanoate, tert-butyl 3,5,5-trimethylperhexanoate, tert-butylperoxy-2-ethylhexyl monocarbonate, and tert-butylperoxymaleic acid.

[0155] Commercially available radical polymerization initiators include, for example, “Perbutyl C”, “Perbutyl A”, “Perbutyl P”, “Perbutyl L”, “Perbutyl O”, “Perbutyl ND”, “Perbutyl Z”, “Perbutyl I”, “Percumyl P”, “Percumyl D”, “Perhexyl D”, “Perhexyl A”, “Perhexyl I”, “Perhexyl Z”, “Perhexyl ND”, “Perhexyl O”, and “Perhexyl PV”, all manufactured by NOF Corporation.

[0156] When the resin composition of the present invention contains a radical polymerization initiator, the content of the radical polymerization initiator in the resin composition is not particularly limited, but when the resin component in the resin composition is taken as 100 mass%, it is preferably 0.01 mass% or more, more preferably 0.02 mass% or more, and even more preferably 0.1 mass% or more, and the upper limit is preferably 3 mass% or less, more preferably 2 mass% or less, and even more preferably 1 mass% or less or 0.5 mass% or less.

[0157] <Optional Additives> The resin composition of the present invention may further contain any additives. Examples of such additives include thermoplastic resins such as phenoxy resins, polyvinyl acetal resins, polysulfone resins, polyethersulfone resins, polyetheretherketone resins, and polyester resins; organic fillers such as rubber particles; organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt 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 bentone and montmorillonite; defoamers such as silicone-based defoamers, acrylic-based defoamers, fluorine-based defoamers, and vinyl resin-based defoamers; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; and bonding agents such as urea silane. Adhesion improvers; 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, phosphazene compounds, phosphinic acid compounds, and 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. The content of such additives may be determined according to the properties required for the resin composition.

[0158] <Organic solvent> The resin composition of the present invention may further contain an organic solvent as a volatile component. Examples of the organic solvent include ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester-based solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone; ether-based solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, and diphenyl ether; alcohol-based solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, and methyl methoxypropionate. Examples of the organic solvent include ether ester solvents such as ethyl 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.

[0159] The resin composition of the present invention can be produced, for example, by adding and mixing an inorganic filler, an oligophenylene ether skeleton-containing resin X, an oligophenylene ether skeleton-containing resin Y, and, if necessary, a thermosetting resin, a curing agent, a curing accelerator, a radical polymerization initiator, other additives, and an organic solvent in any order and / or all at once in any order into any preparation vessel. In addition, the temperature can be appropriately set during the process of adding and mixing each component, and heating and / or cooling may be performed temporarily or throughout. In addition, during or after the process of adding and mixing, the thermosetting resin composition may be stirred or shaken using a stirring device or shaking device such as a mixer to disperse it uniformly. In addition, degassing may be performed under low pressure conditions such as under vacuum at the same time as stirring or shaking.

[0160] As described above, the resin composition of the present invention, which contains a combination of an inorganic filler and oligophenylene ether skeleton-containing resins X and Y, has a low dielectric tangent, exhibits good elongation, and can provide a cured product with excellent uniformity.

[0161] In one embodiment, the cured product of the resin composition of the present invention is characterized by a low dielectric loss tangent (Df). For example, when measured at 5.8 GHz and 23° C. as described in the <Measurement of Dielectric Loss Tangent> section below, the dielectric loss tangent (Df) of the cured product of the resin composition of the present invention can be preferably 0.0040 or less, more preferably 0.0038 or less, even more preferably 0.0036 or less, even more preferably 0.0034 or less, and particularly preferably 0.0032 or less.

[0162] In one embodiment, the cured product of the resin composition of the present invention has a characteristic of exhibiting good elongation. For example, when measured under conditions in accordance with JIS K7127 as described in the <Elongation Evaluation> section below, the elongation (elongation at break) of the cured product of the resin composition of the present invention is preferably 0.9% or more or 1.0% or more, more preferably 1.2% or more or 1.3% or more, and even more preferably 1.5% or more or 1.6% or more, and the upper limit is not particularly limited, but may usually be 5% or less, 4% or less, 3% or less, etc.

[0163] As described above, the resin composition of the present invention can provide a cured product having a low dielectric tangent, good elongation, and excellent uniformity. Therefore, the resin composition of the present invention can be suitably used as a resin composition for forming an encapsulation layer on a semiconductor chip in a semiconductor chip package (a resin composition for semiconductor encapsulation). The resin composition of the present invention can also be suitably used as a resin composition for forming an insulating layer of a printed wiring board (a resin composition for an insulating layer of a printed wiring board), and can be more suitably used as a resin composition for forming an interlayer insulating layer of a printed wiring board (a resin composition for an interlayer insulating layer of a printed wiring board). The resin composition of the present invention can also be suitably used when the printed wiring board is a circuit board with built-in components. The resin composition of the present invention can also be suitably used as a resin composition for forming an insulating layer of a rewiring board in a semiconductor chip package (a resin composition for an insulating layer of a rewiring board). In the present invention, the printed wiring board and the rewiring board are collectively referred to as "circuit board", and therefore the resin composition of the present invention can be suitably used for the insulating layer of a circuit board.

[0164] The resin composition of the present invention can further be used in a wide range of applications requiring a resin composition, such as sheet-like laminate materials such as resin sheets and prepregs, solder resists, underfill materials, die bonding materials, hole filling resins, sealing resins, and component embedding resins.

[0165] [Sheet-type laminated materials (resin sheets, prepregs)] The resin composition of the present invention can be used as it is, but it may also be used in the form of a sheet-like laminate material containing the resin composition.

[0166] As the sheet-like laminate material, the following resin sheets and prepregs are preferred.

[0167] In one embodiment, the resin sheet includes a support and a layer of a resin composition (hereinafter simply referred to as a "resin composition layer") provided on the support, and is characterized in that the resin composition layer is formed from the resin composition of the present invention.

[0168] The thickness of the resin composition layer may vary depending on the application, and may be appropriately determined depending on the application. For example, the thickness of the resin composition layer is preferably 400 μm or less, 300 μm or less, 200 μm or less, 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 from the viewpoint of thinning of printed wiring boards and semiconductor chip packages. The lower limit of the thickness of the resin composition layer is not particularly limited, but may usually be 1 μm or more, 5 μm or more, etc.

[0169] 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. Thus, in a preferred embodiment, the support is a thermoplastic resin film or a metal foil.

[0170] When a thermoplastic resin film is used as the support, examples of the thermoplastic resin include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), acrylics such as polycarbonate (PC) and polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

[0171] When a metal foil is used as the support, examples of the metal foil include copper foil, aluminum foil, etc., and copper foil is preferred. As the copper foil, a foil made of a single metal, copper, or an alloy of copper and another metal (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.

[0172] The support may be subjected to a matte treatment, a corona treatment, or an antistatic treatment on the surface to be bonded to the resin composition layer. In addition, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer may be used as the support. The release agent used in the release layer of the support with a release layer may be, for example, one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. The support with a release layer may be a commercially available product, for example, "SK-1", "AL-5", and "AL-7" manufactured by Lintec Corporation, "Lumirror T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Limited, and "Unipeel" manufactured by Unitika Limited, which are PET films having a release layer mainly composed of an alkyd resin-based release agent.

[0173] The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. When a support with a release layer is used, it is preferable that the total thickness of the support with a release layer is in the above range.

[0174] When a metal foil is used as the support, a metal foil with a support substrate may be used, which is a thin metal foil with a peelable support substrate attached thereto. 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 a metal foil with a support substrate is used as the support, the resin composition layer is provided on the metal foil.

[0175] In the metal foil with a supporting substrate, the material of the supporting substrate is not particularly limited, and examples thereof include copper foil, aluminum foil, stainless steel foil, titanium foil, copper alloy foil, etc. When copper foil is used as the supporting substrate, it may be electrolytic copper foil or rolled copper foil. In addition, the release layer is not particularly limited as long as it can release the metal foil from the supporting substrate, and examples thereof include an alloy layer of an element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, and P; an organic coating, etc.

[0176] In the metal foil with a supporting substrate, the material of the metal foil is preferably, for example, copper foil or copper alloy foil.

[0177] In the metal foil with a supporting substrate, the thickness of the supporting substrate is not particularly limited, but is preferably in the range of 10 μm to 150 μm, more preferably in the range of 10 μm to 100 μm, and the thickness of the metal foil may be, for example, in the range of 0.1 μm to 10 μm.

[0178] In one embodiment, the resin sheet may further include an optional layer as necessary. For example, such an optional layer may be a protective film provided on the surface of the resin composition layer that is not bonded to the support (i.e., the surface opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to suppress adhesion of dirt and the like to the surface of the resin composition layer and scratches.

[0179] The resin sheet can be produced, for example, by preparing a liquid resin composition as is or a resin varnish by dissolving the resin composition in an organic solvent, applying this onto a support using a die coater or the like, and then drying to form a resin composition layer.

[0180] The organic solvent may be the same as the organic solvent described as a component of the resin composition. The organic solvent may be used alone or in combination of two or more kinds.

[0181] Drying may be performed by a known method such as heating or hot air blowing. Drying conditions are not particularly limited, but drying is performed so that the content of the organic solvent in the resin composition layer becomes 10% by mass or less, preferably 5% by mass or less. Although it varies depending on the boiling point of the organic solvent in the resin composition or resin varnish, for example, when a resin composition or resin varnish containing 30% by mass to 60% by mass of the organic solvent is used, the resin composition layer can be formed by drying at 50°C to 150°C for 3 minutes to 10 minutes.

[0182] The resin sheet can be stored in a rolled state. When the resin sheet has a protective film, it can be used by peeling off the protective film.

[0183] In one embodiment, the prepreg is formed by impregnating a sheet-like fiber substrate with the resin composition of the present invention.

[0184] The sheet-like fiber substrate used for the prepreg is not particularly limited, and can be a substrate commonly used for prepreg, such as glass cloth, aramid nonwoven fabric, or liquid crystal polymer nonwoven fabric. From the viewpoint of thinning of printed wiring boards and semiconductor chip packages, the thickness of the sheet-like fiber substrate is preferably 50 μm or less, more preferably 40 μm or less, even more 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. It is usually 10 μm or more.

[0185] The prepreg can be produced by a known method such as a hot melt method or a solvent method.

[0186] The thickness of the prepreg may be in the same range as that of the resin composition layer in the above-mentioned resin sheet.

[0187] The sheet-like laminate material of the present invention can be suitably used to form an encapsulation layer on a semiconductor chip in a semiconductor chip package (for semiconductor encapsulation). The sheet-like laminate material of the present invention can also be suitably used to form an insulating layer of a printed wiring board (for the insulating layer of a printed wiring board), and more suitably used to form an interlayer insulating layer of a printed wiring board (for the interlayer insulating layer of a printed wiring board). The sheet-like laminate material of the present invention can also be suitably used to form an insulating layer of a rewiring board in a semiconductor chip package (for the insulating layer of a rewiring board). That is, the sheet-like laminate material of the present invention can also be suitably used for the insulating layer of a circuit board.

[0188] [Semiconductor chip package] The semiconductor chip package of the present invention comprises a cured product of the resin composition of the present invention.

[0189] In one embodiment, the semiconductor chip package of the present invention includes a package substrate, a semiconductor chip mounted on the substrate, and a cured product of the resin composition of the present invention that encapsulates at least a portion of the semiconductor chip. Hereinafter, such an embodiment is also referred to as "embodiment A."

[0190] In embodiment A, the package substrate may be a conventionally known substrate used for forming a semiconductor chip package, and may be manufactured, for example, in the same manner as the printed wiring board described below.

[0191] The bonding conditions for the packaging substrate and the semiconductor chip may be any conditions that allow conductive connection between the terminal electrodes of the semiconductor chip and the circuit wiring of the substrate, such as the conditions used in flip-chip mounting of the semiconductor chip.

[0192] An example of the bonding method is a method of bonding a semiconductor chip to a substrate. The bonding temperature is usually in the range of 120°C to 240°C (preferably in the range of 130°C to 200°C, more preferably in the range of 140°C to 180°C), and the bonding time is usually in the range of 1 second to 60 seconds (preferably in the range of 5 seconds to 30 seconds). Another example of the bonding method is a method of placing a semiconductor chip on a substrate and bonding it by reflow. The reflow conditions may be in the range of 120°C to 300°C.

[0193] After bonding the semiconductor chip to the substrate, the gap between the semiconductor chip and the substrate may be filled with an underfill material. The resin composition of the present invention can also be used as such an underfill material. In such a case, the semiconductor chip package of the present invention includes an underfill material made of a cured product of the resin composition of the present invention.

[0194] The semiconductor chip can be encapsulated by the same method as step (3) in embodiment B described below. As described above, the resin composition of the present invention is useful as an encapsulant for such semiconductor chips. In such a case, the semiconductor chip package of the present invention includes an encapsulation layer made of a cured product of the resin composition of the present invention.

[0195] The resin composition of the present invention may be used as a mold underfill material to simultaneously fill the gap between a semiconductor chip and a substrate and seal the semiconductor chip.

[0196] When a semiconductor chip package is produced using the resin composition of the present invention, the resin composition of the present invention may be used as a liquid resin composition or in the form of a sheet-like laminate material as described above.

[0197] In another embodiment (hereinafter also referred to as "embodiment B"), the semiconductor chip package of the present invention can be manufactured, for example, by a method including the following steps (1) to (6) using the resin composition of the present invention. The resin composition of the present invention may be used to form the sealing layer in step (3) or the rewiring formation layer in step (5). An example of forming a sealing layer or a rewiring formation layer using a resin composition will be shown below, but the technology for forming the sealing layer or the rewiring formation layer of a semiconductor chip package is publicly known, and a person skilled in the art can manufacture a semiconductor chip package using the resin composition of the present invention according to the publicly known technology. (1) A step of laminating a temporary fixing film onto a substrate; (2) a step of temporarily fixing a semiconductor chip on a temporary fixing film; (3) forming an encapsulation layer on the semiconductor chip; (4) peeling the substrate and the temporary fixing film from the semiconductor chip; (5) forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film have been peeled off; and (6) A process of forming a rewiring layer as a conductor layer on the rewiring formation layer.

[0198] -Process (1)- The material used for the substrate is not particularly limited. Examples of the substrate include silicon wafers, glass wafers, glass substrates, metal substrates such as copper, titanium, stainless steel, and cold-rolled steel (SPCC), substrates in which glass fibers are impregnated with epoxy resin or the like and then heat-cured (e.g., FR-4 substrates), and substrates made of bismaleimide triazine resin (BT resin).

[0199] The material of the temporary fixing film is not particularly limited as long as it can be peeled off from the semiconductor chip in step (4) and can temporarily fix the semiconductor chip. A commercially available product can be used as the temporary fixing film. An example of the commercially available product is Riva Alpha manufactured by Nitto Denko Corporation.

[0200] -Process (2)- The semiconductor chip is temporarily fixed on the temporary fixing film so that the electrode pad surface of the semiconductor chip is bonded to the temporary fixing film. The temporary fixing of the semiconductor chip can be performed using a known device such as a flip chip bonder or a die bonder. The layout and number of the semiconductor chips can be appropriately set according to the shape and size of the temporary fixing film, the number of semiconductor packages to be produced, etc., and the semiconductor chips can be temporarily fixed by arranging them in a matrix shape of multiple rows and multiple columns, for example.

[0201] -Process (3)- The resin composition of the present invention is applied as a liquid composition onto a semiconductor chip and cured (for example, thermally cured) to form an encapsulating layer. Alternatively, the resin composition of the present invention may be laminated on a semiconductor chip in the form of the above-mentioned resin sheet and cured (for example, thermally cured) to form an encapsulating layer.

[0202] When used in the form of a resin sheet, the semiconductor chip and the resin sheet can be laminated by removing the protective film of the resin sheet and then heat-pressing the resin sheet to the semiconductor chip from the support side. The semiconductor chip and the resin sheet can be laminated by a vacuum lamination method, and the lamination conditions are the same as those described later in relation to the manufacturing method of the printed wiring board, and the preferred ranges are also the same.

[0203] After lamination, the resin composition is thermally cured to form the encapsulating layer under the same conditions as those described below in relation to the method for producing a printed wiring board.

[0204] The support of the resin sheet may be peeled off after the resin sheet is laminated on the semiconductor chip and thermally cured, or the support may be peeled off before the resin sheet is laminated on the semiconductor chip.

[0205] When the resin composition of the present invention is applied as a liquid composition to form a sealing layer, the application conditions may be the same as those for forming the resin composition layer described in relation to the resin sheet of the present invention. By using the resin composition of the present invention, good fluidity can be achieved at the application and molding temperature.

[0206] -Process (4)- The method for peeling off the substrate and the temporary fixing film can be appropriately changed depending on the material of the temporary fixing film, and examples of the method include a method in which the temporary fixing film is heated and foamed (or expanded) to peel it off, and a method in which ultraviolet light is irradiated from the substrate side to reduce the adhesive strength of the temporary fixing film and then peeled off.

[0207] In the method of heating and foaming (or expanding) the temporary fixing film to peel it off, the heating conditions are usually 100 to 250° C. for 1 to 90 seconds or 5 to 15 minutes. In the method of irradiating ultraviolet light from the substrate side to reduce the adhesive strength of the temporary fixing film to peel it off, the irradiation dose of ultraviolet light is usually 10 mJ / cm. 2 ~1000mJ / cm 2 It is.

[0208] -Process (5)- The material for forming the rewiring formation layer (insulating layer) is not particularly limited as long as it has insulating properties when the rewiring formation layer (insulating layer) is formed, and from the viewpoint of ease of manufacturing the semiconductor chip package, a photosensitive resin or a thermosetting resin is preferred. The resin composition of the present invention can also be suitably used for forming the rewiring formation layer.

[0209] After forming the redistribution layer, a via hole may be formed in the redistribution layer to connect the semiconductor chip to a conductor layer described later. The via hole may be formed by a known method depending on the material of the redistribution layer.

[0210] -Process (6)- The material of the conductor layer formed on the rewiring formation layer is not particularly limited. In a preferred embodiment, the conductor layer contains one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. The conductor layer may be a single metal layer or an alloy layer, and examples of the alloy layer include layers formed from alloys of two or more metals selected from the above group (e.g., nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy). Among them, from the viewpoints of versatility, cost, ease of patterning, etc. of the conductor layer formation, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of a nickel-chromium alloy, a copper-nickel alloy or a copper-titanium alloy is preferred, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of a nickel-chromium alloy is more preferred, and a single metal layer of copper is even more preferred.

[0211] The conductor layer may be a single-layer structure or a multi-layer structure in which two or more single metal layers or alloy layers made of different kinds of metals or alloys are laminated. When the conductor layer has a 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 a nickel-chromium alloy.

[0212] The thickness of the conductor layer depends on the desired design of the semiconductor chip package, but is generally 1 μm to 35 μm, preferably 1 μm to 20 μm.

[0213] In one embodiment, the conductor layer may be formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating the surface of the rewiring formation layer by a conventionally known technique such as a semi-additive method or a full-additive method, and from the viewpoint of ease of production, it is preferable to form the conductor layer by the semi-additive method. Below, an example of forming the conductor layer by the semi-additive method is shown.

[0214] First, a plating seed layer is formed on the surface of the rewiring formation layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer to expose a part of the plating seed layer corresponding to a desired wiring pattern. After a metal layer is formed on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. Thereafter, unnecessary plating seed layer is removed by etching or the like to form a conductor layer (rewiring layer) having a desired wiring pattern.

[0215] The steps (5) and (6) may be repeated to alternately stack (build up) conductive layers (rewiring layers) and rewiring formation layers (insulating layers).

[0216] In manufacturing the semiconductor chip package, the steps of (7) forming a solder resist layer on the conductor layer (rewiring layer), (8) forming bumps, and (9) dicing and singulating a plurality of semiconductor chip packages into individual semiconductor chip packages may be further performed. These steps may be performed according to various methods used in manufacturing semiconductor chip packages and known to those skilled in the art.

[0217] The above-mentioned embodiment B is a method of forming a rewiring layer on the electrode pad surface of a semiconductor chip first, i.e., chip 1st (Chip-1 st In addition to the chip 1st process, the semiconductor chip package of the present invention can also be manufactured by a process in which a rewiring layer is first provided, and then a semiconductor chip is provided on the rewiring layer in such a state that the electrode pad surface of the semiconductor chip can be electrically connected to the rewiring layer, and then the semiconductor chip is sealed. stThe resin composition of the present invention may be produced by the Chip-1 st Construction method and RDL-1 st Regardless of the construction method, it is possible to realize a semiconductor chip package with extremely low transmission loss, which is required for next-generation high-speed communication applications.

[0218] By forming an encapsulation layer, a rewiring formation layer, etc. using the resin composition of the present invention, which has a low dielectric tangent, good elongation, and provides a cured product with excellent uniformity, a semiconductor chip package with extremely low transmission loss can be realized regardless of whether the semiconductor package is a fan-in type package or a fan-out type package. In one embodiment, the semiconductor chip package of the present invention is a fan-out type package. The resin composition of the present invention can be applied to both a fan-out type panel level package (FOPLP) and a fan-out type wafer level package (FOWLP). In one embodiment, the semiconductor package of the present invention is a fan-out type panel level package (FOPLP). In another embodiment, the semiconductor package of the present invention is a fan-out type wafer level package (FOWLP).

[0219] [Printed wiring board] A printed wiring board can be produced using the resin composition of the present invention. The present invention also provides such a printed wiring board. The printed wiring board of the present invention is characterized by including an insulating layer made of a cured product of the resin composition of the present invention.

[0220] The printed wiring board can be produced, for example, by using the above-mentioned resin sheet, by a method including the following steps (I) and (II). (I) A step of laminating a resin sheet on an inner layer substrate such that a resin composition layer of the resin sheet is bonded to the inner layer substrate. (II) A step of curing (e.g., heat curing) the resin composition layer to form an insulating layer.

[0221] The "inner layer substrate" used in step (I) is a member that becomes the substrate of the printed wiring board, and examples thereof include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. The substrate may have a conductor layer on one or both sides, 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 may be called an "inner layer circuit substrate". In addition, an intermediate product on which an insulating layer and / or a conductor layer is to be formed during the manufacture of a printed wiring board is also included in the "inner layer substrate" of the present invention. When the printed wiring board is a circuit board with built-in components, an inner layer substrate with built-in components may be used.

[0222] 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. Examples of the member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter also referred to as the "thermocompression bonding member") include a heated metal plate (such as a SUS plate) or a metal roll (SUS roll). The thermocompression bonding member may be pressed directly onto the resin sheet, or may be pressed via an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently follow the surface irregularities of the inner layer substrate.

[0223] The lamination of the inner layer substrate and the resin sheet may be performed by a vacuum lamination method. In the vacuum lamination method, the thermocompression temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, the thermocompression pressure is preferably in the range of 0.098MPa to 1.77MPa, more preferably in the range of 0.29MPa to 1.47MPa, and the thermocompression 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 may be performed under reduced pressure conditions, preferably at a pressure of 26.7hPa or less.

[0224] The lamination can be performed by a commercially available vacuum laminator, such as a vacuum pressure laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum applicator manufactured by Nikko Materials Co., Ltd., or a batch type vacuum pressure laminator.

[0225] After lamination, the laminated resin sheet may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression member from the support side. The pressing conditions for the smoothing treatment may be the same as the thermocompression conditions for the lamination. The smoothing treatment may be performed using a commercially available laminator. The lamination and smoothing treatment may be performed consecutively using the commercially available vacuum laminator.

[0226] The support may be removed between step (I) and step (II), or after step (II). When a metal foil is used as the support, the conductor layer may be formed using the metal foil without peeling off the support. When a metal foil with a support substrate is used as the support, the support substrate (and the peel layer) may be peeled off. Then, the conductor layer can be formed using the metal foil.

[0227] In step (II), the resin composition layer is cured (for example, thermally cured) to form an insulating layer made of a cured product of the resin composition. The curing conditions for the resin composition layer are not particularly limited, and conditions that are usually adopted when forming an insulating layer for a printed wiring board may be used.

[0228] For example, the thermal curing conditions for the resin composition layer vary depending on the type of resin composition, etc., but in one embodiment, the curing temperature is preferably 120° C. to 250° C., more preferably 150° C. to 240° C., and even more preferably 180° C. to 230° C. The curing time can be preferably 5 minutes to 240 minutes, more preferably 10 minutes to 150 minutes, and even more preferably 15 minutes to 120 minutes.

[0229] Before the resin composition layer is thermally cured, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature of 50° C. to 120° C., preferably 60° C. to 115° C., more preferably 70° C. to 110° C. for 5 minutes or more, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and even more preferably 15 minutes to 100 minutes.

[0230] In manufacturing a printed wiring board, the steps of (III) drilling holes in the insulating layer, (IV) roughening the insulating layer, and (V) forming a conductor layer may be further carried out. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art that are used in manufacturing printed wiring boards. When the support is removed after step (II), the removal of the support may be carried out 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) may be repeated to form a multilayer wiring board, as necessary.

[0231] In another embodiment, the printed wiring board can be manufactured using the above-mentioned prepreg. The manufacturing method is basically the same as when the resin sheet is used.

[0232] Step (III) is a step of drilling holes in the insulating layer, which allows holes such as via holes and through holes to be formed in the insulating layer. Step (III) may be performed using, for example, a drill, a laser, plasma, etc., depending on the composition of the resin composition used to form the insulating layer. The dimensions and shape of the holes may be appropriately determined depending on the design of the printed wiring board.

[0233] Step (IV) is a step of roughening the insulating layer. Usually, in this step (IV), smear removal (desmear) is also performed. The procedure and conditions of the roughening treatment are not particularly limited, and known procedures and conditions that are usually used when forming an insulating layer of a printed wiring board can be adopted. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order.

[0234] The swelling liquid used in the roughening treatment is not particularly limited, but includes an alkaline solution, a surfactant solution, etc., and is preferably an alkaline solution, and more preferably a sodium hydroxide solution or a potassium hydroxide solution. Examples of commercially available swelling liquids include "Swelling Dip Securigans P" and "Swelling Dip Securigans SBU" manufactured by Atotech Japan. The swelling treatment using the swelling liquid is not particularly limited, but can be performed by immersing the insulating layer in a swelling liquid at 30°C to 90°C for 1 to 20 minutes, for example. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40°C to 80°C for 5 to 15 minutes.

[0235] The oxidizing agent used in the roughening treatment is not particularly limited, but examples thereof include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment using an oxidizing agent such as an alkaline permanganate solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60°C to 100°C for 10 minutes to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securigans P" manufactured by Atotech Japan.

[0236] The neutralizing solution used in the roughening treatment is preferably an acidic aqueous solution, and a commercially available product such as "Reduction Solution Securigant P" manufactured by Atotech Japan can be mentioned.

[0237] The treatment with the neutralizing solution can be carried out by immersing the surface that has been roughened with an oxidizing agent in a neutralizing solution at 30° C. to 80° C. for 5 to 30 minutes. From the viewpoint of workability, etc., a method in which the object that has been roughened with an oxidizing agent is immersed in a neutralizing solution at 40° C. to 70° C. for 5 to 20 minutes is preferred.

[0238] Step (V) is a step of forming a conductor layer on an insulating layer, and may be performed in the same manner as step (6) described in relation to the method for manufacturing a semiconductor chip package.

[0239] The thickness of the conductor layer depends on the desired design of the printed wiring board, but is generally 3 μm to 35 μm, and preferably 5 μm to 30 μm.

[0240] The conductor layer may also be formed using a metal foil. When the conductor layer is formed using a metal foil, it is preferable to carry out step (V) between steps (I) and (II). For example, after step (I), the support is removed, and a metal foil is laminated on the exposed surface of the resin composition layer. The lamination of the resin composition layer and the metal foil may be carried out by a vacuum lamination method. The lamination conditions may be the same as those described for step (I). Then, step (II) is carried out to form an insulating layer. Thereafter, a conductor layer having a desired wiring pattern can be formed by a conventionally known technique such as a subtractive method or a modified semi-additive method, using the metal foil on the insulating layer.

[0241] The metal foil can be produced by a known method such as an electrolytic method, a rolling method, etc. Commercially available metal foils include, for example, HLP foil and JXUT-III foil manufactured by JX Nippon Mining & Metals Corporation, and 3EC-III foil and TP-III foil manufactured by Mitsui Mining & Smelting Co., Ltd.

[0242] Alternatively, when a metal foil or a metal foil with a supporting substrate is used as the support for the resin sheet, the conductor layer may be formed using the metal foil, as described above.

[0243] [Semiconductor Devices] The semiconductor device of the present invention includes a layer made of a cured product of the resin composition of the present invention. The semiconductor device of the present invention can be manufactured using the semiconductor chip package or printed wiring board of the present invention.

[0244] Examples of the semiconductor device include various semiconductor devices used in electric appliances (for example, computers, mobile phones, digital cameras, and televisions) and vehicles (for example, motorcycles, automobiles, trains, ships, and aircraft). EXAMPLES

[0245] The present invention will be specifically described below with reference to examples. The present invention is not limited to these examples. In the following, "parts" representing amounts means "parts by mass" unless otherwise specified.

[0246] <Synthesis Example 1: Synthesis of Resin X1> A reaction vessel was charged with 112 g of bifunctional hydroxyl-terminated polybutadiene ("G-3000" manufactured by Nippon Soda Co., Ltd., number average molecular weight = 3000, hydroxyl group equivalent = 1800 g / eq.), 272 g of anisole as a solvent, and 14 g of isophorone diisocyanate (IPDI), and the temperature was raised to 50°C to carry out the reaction for approximately 1 hour. Next, 145 g of oligophenylene ether resin containing phenolic hydroxyl groups at both ends ("SA90-100" manufactured by Sabic, hydroxyl group equivalent = 800 g / eq.) and 1 g of benzophenonetetracarboxylic dianhydride (BTDA) were added to the reaction mixture, and the mixture was heated to 140°C with stirring and reacted for about 4 hours. -1 The disappearance of the NCO peak was confirmed. The disappearance of the NCO peak was regarded as the end of the reaction, and the reaction product was cooled to room temperature. The reaction product was then filtered through a 100-mesh filter cloth to obtain Resin X1 having an oligophenylene ether skeleton (non-volatile content 50% by mass, viscosity at 25°C 6.0 Pa s, weight-average molecular weight 280,000, glass transition temperature 0°C).

[0247] <Synthesis Example 2: Synthesis of Resin X2> A reaction vessel was charged with 60 g of bifunctional hydroxyl-terminated polybutadiene ("G-1000" manufactured by Nippon Soda Co., Ltd., number average molecular weight = 1400, hydroxyl group equivalent = 800 g / eq.), 220 g of anisole as a solvent, and 14 g of isophorone diisocyanate (IPDI), and the temperature was raised to 50°C to carry out the reaction for approximately 1 hour. Next, 145 g of oligophenylene ether resin containing phenolic hydroxyl groups at both ends ("SA90-100" manufactured by Sabic, hydroxyl group equivalent = 800 g / eq.) and 1 g of benzophenonetetracarboxylic dianhydride (BTDA) were added to the reaction mixture, and the mixture was heated to 140°C with stirring and reacted for about 4 hours. -1 The disappearance of the NCO peak was confirmed. The disappearance of the NCO peak was regarded as the end of the reaction, and the reaction product was cooled to room temperature. The reaction product was then filtered through a 100-mesh filter cloth to obtain Resin X2 having an oligophenylene ether skeleton (non-volatile content 50% by mass, viscosity at 25°C 2.0 Pa s, weight-average molecular weight 260,000, glass transition temperature 0°C).

[0248] <Synthesis Example 3: Synthesis of Resin X3> A reaction vessel was charged with 83 g of polycarbonate diol ("C-2015N" manufactured by Kuraray Co., Ltd., number average molecular weight = 2000, hydroxyl group equivalent = 1000 g / eq.), 240 g of anisole as a solvent, and 14 g of isophorone diisocyanate (IPDI), and the temperature was raised to 50°C and the reaction was carried out for about 1 hour. Next, 145 g of oligophenylene ether resin containing phenolic hydroxyl groups at both ends ("SA90-100" manufactured by Sabic, hydroxyl group equivalent = 800 g / eq.) and 1 g of benzophenonetetracarboxylic dianhydride (BTDA) were added to the reaction mixture, and the mixture was heated to 140°C with stirring and reacted for about 4 hours. -1 The disappearance of the NCO peak was confirmed. The disappearance of the NCO peak was regarded as the end of the reaction, and the reaction mixture was cooled to room temperature. The reaction mixture was then filtered through a 100-mesh filter cloth to obtain Resin X3 having an oligophenylene ether skeleton (non-volatile content 50% by mass, viscosity at 25°C 4.0 Pa s, weight-average molecular weight 254,000, glass transition temperature -4°C).

[0249] [Examples 1 to 9, Comparative Examples 1 to 3] (1) Preparation of resin composition Each component was weighed according to the compounding composition shown in Table 1, and then 15 parts of MEK was added and mixed, followed by uniform dispersion using a high-speed rotating mixer to obtain a resin composition (resin varnish).

[0250] (2) Manufacturing of resin sheets A polyethylene terephthalate film with a release layer ("AL5" manufactured by Lintec Corporation, thickness 38 μm) was prepared as a support. The obtained resin varnish was uniformly applied onto the release layer of this support so that the thickness of the resin composition layer after drying would be 50 μm. Thereafter, the resin composition was dried at 80°C to 120°C (average 100°C) for 4 minutes to obtain a resin sheet having a layer structure of a resin composition layer / support.

[0251] <Evaluation of elongation> The resin sheets obtained in the Examples and Comparative Examples were heated at 200° C. for 90 minutes to thermally cure the resin composition layers. Next, the support was peeled off to obtain a cured product of the resin composition layer. This cured product was subjected to a tensile test in accordance with Japanese Industrial Standards (JIS K7127) using a Tensilon universal testing machine ("RTC-1250A" manufactured by Orientec Co., Ltd.) to measure the elongation at break (%) at 23°C and evaluate according to the following criteria. ×: Elongation at break is less than 0.9% △: Elongation at break is 0.9% or more and less than 1.2% ◯: Elongation at break is 1.2% or more

[0252] <Evaluation of Unevenness> The resin sheets obtained in the examples and comparative examples were visually observed to check for the presence or absence of surface unevenness, and were evaluated according to the following criteria. 〇: No unevenness and the surface is uniform ×: Uneven

[0253] <Measurement of dielectric tangent> The resin sheets obtained in the examples and comparative examples were heated at 200°C for 90 minutes to thermally cure the resin composition layer. The support was then peeled off to obtain a cured product of the resin composition layer. The cured product was cut into a length of 80 mm and a width of 2 mm to prepare a test piece for evaluation. The dielectric loss tangent (Df value) of each evaluation specimen was measured by the cavity resonance perturbation method using Agilent Technologies' "HP8362B" at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C. Measurements were performed on three specimens, and the average value was calculated. The obtained average value was evaluated according to the following criteria. Evaluation criteria ×: Dielectric tangent is 0.005 or more △: Dielectric tangent is over 0.004 and less than 0.005 ○: Dielectric tangent is 0.004 or less

[0254] The results of Examples 1 to 9 and Comparative Examples 1 to 3 are shown in Table 1.

[0255] [Table 1]

[0256] The details of each component listed in Table 1 are as follows. <Thermosetting resin> 828EL: Bisphenol A type epoxy resin, functional group equivalent weight approx. 180g / eq, manufactured by Mitsubishi Chemical Corporation HP-6000L: Naphthylene ether type epoxy resin, functional group equivalent weight approx. 213g / eq, manufactured by DIC Corporation YX4000H: Biphenyl type epoxy resin, functional group equivalent 190g / eq, manufactured by Mitsubishi Chemical Corporation <Hardening agent> KA-1160: Phenol-based hardener, cresol novolac resin, functional group equivalent 117g / eq, manufactured by DIC HPC-8000-65T: Active ester curing agent, functional group equivalent weight 223g / eq, non-volatile content 65% by mass in toluene solution, manufactured by DIC Corporation V-03: Carbodiimide curing agent, functional group equivalent weight 216g / eq, non-volatile content 50% by mass in toluene solution, manufactured by Nisshinbo Chemical Co., Ltd. <Resin X> Resins X1 to X3: Resins X1 to X3 synthesized in Synthesis Examples 1 to 3, toluene solutions with 65% non-volatile content <Resin Y> SA90: Resin containing oligophenylene ether skeleton, weight average molecular weight 4400, manufactured by SABIC SA9000: Resin containing oligophenylene ether skeleton, weight average molecular weight 3900, manufactured by SABIC OPE-2St-1200: Resin containing oligophenylene ether skeleton, weight average molecular weight 3000, non-volatile content 65% by mass in toluene solution, manufactured by Mitsubishi Gas Chemical Co., Ltd. X-12-1288C: Oligophenylene ether skeleton-containing resin, weight average molecular weight 3600, toluene solution with non-volatile content of 20% by mass, manufactured by Shin-Etsu Chemical Co., Ltd. X-12-1288D: Oligophenylene ether skeleton resin, weight average molecular weight 3500, toluene solution with non-volatile content of 20% by mass, manufactured by Shin-Etsu Chemical Co., Ltd. <Curing accelerator> 2P4MZ: Imidazole derivative, manufactured by Shikoku Chemical Industry Co., Ltd. DMAP: 4-Dimethylaminopyridine <Radical polymerization initiator> Dicumyl peroxide: Mitsui Fine Chemicals <Thermoplastic resin> YX7553BH30: Phenoxy resin, 30% non-volatile MEK solution and 1:1 mixed solution of cyclohexanone, manufactured by Mitsubishi Chemical Corporation <Inorganic filler> SO-C2: Spherical silica surface-treated with an amino-silane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), average particle size 0.5μm, specific surface area 5.8m2 / g, manufactured by Admatechs Co., Ltd.

Claims

1. inorganic filler, An oligophenylene ether skeleton-containing resin X having a weight average molecular weight Mw of MC, and Oligophenylene ether skeleton-containing resin Y having a weight average molecular weight Mw of MD A resin composition comprising: <Condition 1> 1,000,000>MC>5MD>500

2. inorganic filler, An oligophenylene ether skeleton-containing resin X having a glass transition temperature of 25° C. or lower, and Resin Y containing an oligophenylene ether skeleton different from resin X A resin composition comprising:

3. 3. The resin composition according to claim 1, wherein the total content of resin X and resin Y is 20% by mass or more and less than 70% by mass, when the resin components in the resin composition are taken as 100% by mass.

4. The resin composition according to claim 1 , wherein the content of the inorganic filler is 50% by mass or more when the nonvolatile components in the resin composition are taken as 100% by mass.

5. 3. The resin composition according to claim 1, wherein the resin X comprises one or more structural units selected from the group consisting of a polyolefin structural unit, a polycarbonate structural unit, a polyether structural unit, a polyester structural unit, a poly(meth)acrylic structural unit, and a polysiloxane structural unit.

6. The resin composition according to claim 1 or 2, further comprising a thermosetting resin.

7. The resin composition according to claim 1 or 2, which is used for semiconductor encapsulation.

8. The resin composition according to claim 1 or 2, which is for use in an insulating layer of a circuit board.

9. A cured product of the resin composition according to claim 1 or 2.

10. A resin sheet comprising a support and a layer of the resin composition according to claim 1 or 2 provided on the support.

11. The resin sheet according to claim 10 , wherein the support is a thermoplastic resin film or a metal foil.

12. A semiconductor chip package comprising an encapsulating layer made of a cured product of the resin composition according to claim 1 or 2.

13. A circuit board comprising an insulating layer made of a cured product of the resin composition according to claim 1 or 2.

14. A semiconductor device comprising the semiconductor chip package according to claim 12.

15. A semiconductor device comprising the circuit board according to claim 13.

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