Compound

Abstract

To provide, e.g., a compound capable of forming a cured product with a high glass transition temperature (Tg).SOLUTION: The invention provides a compound represented by the formula (A-1).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a compound. Furthermore, the present invention relates to a resin composition, a resin sheet, a printed wiring board, and a semiconductor device obtained using the compound.

Background Art

[0002] In general, a printed wiring board is provided with an insulating layer, and the insulating layer is formed by curing a resin composition. As such a resin composition, for example, the resin composition disclosed in Patent Document 1 is known.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] The insulating layer of a printed wiring board is required to have a high glass transition temperature (Tg) from the viewpoint of improving heat resistance.

[0005] An object of the present invention is to provide a compound that provides a cured product having a high glass transition temperature (Tg); a resin composition containing the compound; a resin sheet including a resin composition layer containing the resin composition; a printed wiring board including an insulating layer formed of a cured product of the resin composition; and a semiconductor device including the printed wiring board.

Means for Solving the Problems

[0006] As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by a compound having a predetermined structure, and have completed the present invention.

[0007] That is, the present invention includes the following. [1] A compound represented by the following formula (A-1). [Chemical formula] (In formula (A-1), R 1 and R 2 each independently represent a monovalent aromatic group which may have a substituent, X each independently represents an oxygen atom or a sulfur atom, A each independently represents one or more groups selected from the group represented by the following formula (A-2) and formula (A-3), n represents the number of repetitions and satisfies 0 ≦ n ≦ 8.) [Chemical formula] (In formula (A-2), R 11 and R 12 each independently represent a divalent aromatic group which may have a substituent, L 11 each independently represents a single bond or a divalent linking group which may have a substituent, R 11 and L 11 may combine together to form a ring.) a represents a number in the range of 0 to 5.) [Chemical formula] (In formula (A-3), R 13 and R 14 each independently represent a divalent aromatic group which may have a substituent, L 12 represents a group represented by formula (A-4). b and c each independently represent a number in the range of 0 to 5.) [Chemical formula] (In formula (A-4), R 15 and R 16each independently represents a divalent aromatic group which may have a substituent; L 13 each independently represents a single bond or a divalent linking group which may have a substituent; R 15 and L 13 may combine together to form a ring. d represents a number in the range of 0 to 5.) [2] In formula (A-1), R 1 and R 2 each independently represent a phenyl group which may have a substituent, or a naphthyl group which may have a substituent, the compound according to [1]. [3] In formula (A-2) and formula (A-3), R 11 , R 12 , R 13 , and R 14 each independently represent a phenylene group which may have a substituent, or a naphthylene group which may have a substituent, the compound according to [1] or [2]. [4] In formula (A-4), R 15 , and R 16 each independently represent a phenylene group which may have a substituent, or a naphthylene group which may have a substituent, the compound according to any one of [1] to [3]. [5] In formula (A-2), L 11 each independently represents a single bond, a divalent aliphatic group which may have a substituent, an oxygen atom, a divalent aromatic group which may have a substituent, a carbonyl group, and a sulfonyl group, the compound according to any one of [1] to [4]. [6] In formula (A-2), L 11 each independently represents a single bond, a divalent aliphatic group which may have a substituent, an oxygen atom, a phenylene group, a fluorenylidene group, a carbonyl group, or a sulfonyl group, the compound according to any one of [1] to [5]. [7] The compound according to any one of [1] to [6], wherein X in formula (A-1) represents an oxygen atom. [8] The compound according to any one of [1] to [7], wherein X in formula (A-1) represents an oxygen atom, has a furan skeleton, and carbonyl groups are bonded to the 2-position and 5-position of the furan skeleton, and the biomass ratio of the compound is 10% by mass or more. [9] The compound according to any one of [1] to [8], wherein X in formula (A-1) represents a sulfur atom.

[10] The compound according to any one of [1] to [9], wherein A in formula (A-1) represents one or more groups selected from the groups represented by the following formulas (1a) to (4a).

Chemical formula

[11] The compound according to any one of [1] to

[10] , having a number average molecular weight of 5000 or less.

[12] The compound according to any one of [1] to

[11] , having an active group equivalent of 100 g / eq. or more.

[13] (A) The compound according to any one of [1] to

[12] , (B) A thermosetting resin, and (C) An inorganic filler, a resin composition containing the same.

[14] The resin composition according to

[13] , which is for forming an insulating layer.

[15] A resin sheet including a support and a resin composition layer provided on the support and containing the resin composition according to

[13] or

[14] .

[16] A printed wiring board including an insulating layer formed by a cured product of the resin composition according to

[13] or

[14] .

[17] A semiconductor device including the printed wiring board according to

[16] .

Advantages of the Invention

[0008] According to the present invention, a compound that provides a cured product with a high glass transition temperature (Tg); a resin composition containing the compound; a resin sheet including a resin composition layer containing the resin composition; a printed wiring board including an insulating layer formed of a cured product of the resin composition; and a semiconductor device including the printed wiring board; can be provided.

Brief Description of the Drawings

[0009]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

Figure 9

Figure 10

Embodiments for Carrying Out the Invention

[0010] Hereinafter, the present invention will be described with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples shown below, and can be arbitrarily modified and implemented without departing from the scope of the claims of the present invention and its equivalent scope.

[0011] As used herein, the term "optionally substituted" with respect to a compound or group means both the case where a hydrogen atom of the compound or group is unsubstituted with a substituent and the case where some or all of the hydrogen atoms of the compound or group are substituted with a substituent.

[0012] As used herein, the term "substituent" means, unless otherwise specified, a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl 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, an acyl group, an acyloxy group, a carboxy group, a sulfo group, a cyano group, a nitro group, a hydroxy group, a mercapto group, and an oxo group.

[0013] Examples of the halogen atom used as a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0014] The alkyl group used as a substituent may be either linear or branched. The number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 14, still more preferably 1 to 12, even more preferably 1 to 6, and particularly preferably 1 to 3. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group.

[0015] The number of carbon atoms of the cycloalkyl group used as a substituent is preferably 3 to 20, more preferably 3 to 12, still more preferably 3 to 10, and particularly preferably 3 to 6. Examples of the cycloalkyl group include a camphanil group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

[0016] 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 20, more preferably 1 to 12, and still more preferably 1 to 6. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, a sec-butoxy group, an isobutoxy group, a tert-butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a nonyloxy group, and a decyloxy group.

[0017] The alkenyl group used as a substituent is a monovalent unsaturated hydrocarbon group having one carbon-carbon double bond, and may be either linear or branched. The number of carbon atoms in the alkenyl group is preferably 2 to 20, more preferably 2 to 12, and still more preferably 2 to 6. Examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, and a decenyl group.

[0018] The number of carbon atoms in the cycloalkyloxy group used as a substituent is preferably 3 to 20, more preferably 3 to 12, and still more preferably 3 to 6. Examples of the cycloalkyloxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, and a cyclohexyloxy group.

[0019] The aryl group used as a substituent is a group obtained by removing one hydrogen atom from the aromatic ring of an aromatic hydrocarbon. The number of carbon atoms in the aryl group used as a substituent is preferably 6 to 24, more preferably 6 to 18, still more preferably 6 to 14, and even more preferably 6 to 10. Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, and a benzyl group.

[0020] The number of carbon atoms of the aryloxy group used as a substituent is preferably 6 to 24, more preferably 6 to 18, still more preferably 6 to 14, and even more preferably 6 to 10. Examples of the aryloxy group used as a substituent include a phenoxy group, a 1-naphthyloxy group, and a 2-naphthyloxy group.

[0021] The number of carbon atoms of the arylalkyl group used as a substituent is preferably 7 to 25, more preferably 7 to 19, still more preferably 7 to 15, and even more preferably 7 to 11. Examples of the arylalkyl group include phenyl-C1~C 12 alkyl group, naphthyl-C1~C 12 alkyl group, and anthracenyl-C1~C 12 alkyl group.

[0022] The number of carbon atoms of the arylalkoxy group used as a substituent is preferably 7 to 25, more preferably 7 to 19, still more preferably 7 to 15, and even more preferably 7 to 11. Examples of the arylalkoxy group include phenyl-C1~C 12 alkoxy group, and naphthyl-C1~C 12 alkoxy group.

[0023] The monovalent heterocyclic group used as a substituent refers to a group obtained by removing one hydrogen atom from a heterocycle of a heterocyclic compound. The number of carbon atoms of the monovalent heterocyclic group is preferably 3 to 21, more preferably 3 to 15, and still more preferably 3 to 9. The monovalent heterocyclic group includes a monovalent aromatic heterocyclic group (heteroaryl group). Examples of the monovalent heterocyclic group include a thienyl group, a pyrrolyl group, a furanyl group, a furyl group, a pyridyl group, a pyridazinyl group, a pyrimidinyl group, a pyrazinyl group, a triazinyl group, a pyrrolidyl group, a piperidyl group, a quinolyl group, and an isoquinolyl group.

[0024] The alkylidene group used as a substituent refers to a group obtained by removing two hydrogen atoms from the same carbon atom of an alkane. The number of carbon atoms in the alkylidene group is preferably 1 to 20, more preferably 1 to 14, still more preferably 1 to 12, even more preferably 1 to 6, and particularly preferably 1 to 3. Examples of the alkylidene group include a methylidene group, an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, a sec-butylidene group, an isobutylidene group, a tert-butylidene group, a pentylidene group, a hexylidene group, a heptylidene group, an octylidene group, a nonylidene group, and a decylidene group.

[0025] The acyl group used as a substituent refers to a group represented by the formula: -C(=O)-R (wherein R is an alkyl group or an aryl group). The alkyl group represented by R may be either linear or branched. Examples of the aryl group represented by R include a phenyl group, a naphthyl group, and an anthracenyl group. The number of carbon atoms in the acyl group is preferably 2 to 20, more preferably 2 to 13, and still more preferably 2 to 7. Examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, and a benzoyl group.

[0026] The acyloxy group used as a substituent refers to a group represented by the formula: -O-C(=O)-R (wherein R is an alkyl group or an aryl group). The alkyl group represented by R may be either linear or branched. Examples of the aryl group represented by R include a phenyl group, a naphthyl group, and an anthracenyl group. The number of carbon atoms in the acyloxy group is preferably 2 to 20, more preferably 2 to 13, and still more preferably 2 to 7. Examples of the acyloxy group include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a pivaloyloxy group, and a benzoyloxy group.

[0027] The above-mentioned substituents may further have a substituent (hereinafter sometimes referred to as a "secondary substituent"). Unless otherwise specified, the same substituents as those described above may be used as the secondary substituent.

[0028] [Compound] The compound of the present invention is represented by the following formula (A-1). [Chemical formula] (In formula (A-1), R 1 and R 2 each independently represent a monovalent aromatic group which may have a substituent, X each independently represents an oxygen atom or a sulfur atom, A each independently represents one or more groups selected from the group represented by the following formula (A-2) and formula (A-3), n represents the number of repetitions and satisfies 0 ≦ n ≦ 8.) [Chemical formula] (In formula (A-2), R 11 , and R 12 each independently represent a divalent aromatic group which may have a substituent, L 11 each independently represents a single bond or a divalent linking group which may have a substituent, R 11 and L 11 may combine together to form a ring.) a represents a number in the range of 0 to 5.) [Chemical formula] (In formula (A-3), R 13 , and R 14 each independently represent a divalent aromatic group which may have a substituent, L 12 represents a group represented by formula (A-4). b and c each independently represent a number in the range of 0 to 5.) [Chemical formula] (In formula (A-4), R15 and R 16 each independently represents a divalent aromatic group which may have a substituent, L 13 each independently represents a single bond or a divalent linking group which may have a substituent, R 15 and L 13 may combine together to form a ring. d represents a number in the range of 0 to 5.)

[0029] The compound of the present invention can provide a cured product having a high glass transition temperature (Tg). Hereinafter, the compound of the present invention will be described in detail.

[0030] In formula (A-1), R 1 and R 2 each independently represents a monovalent aromatic group which may have a substituent. The monovalent aromatic group refers to a group obtained by removing one hydrogen atom from an aromatic ring of an aromatic compound. Further, the "aromatic ring" means a ring that follows the Hückel's rule in which the number of electrons contained in the π electron system on the ring is 4n + 2 (n is a natural number), and includes a monocyclic aromatic ring and a condensed aromatic ring in which two or more monocyclic aromatic rings are condensed. The aromatic ring may be a carbocyclic ring or a heterocyclic ring. Examples of the monovalent aromatic group which may have a substituent include an aryl group which may have a substituent and a heteroaryl group which may have a substituent. The number of carbon atoms of the monovalent aromatic group is preferably 3 or more, more preferably 4 or more or 5 or more, still more preferably 6 or more, and the upper limit thereof is preferably 24 or less, more preferably 18 or less or 14 or less, still more preferably 10 or less. The number of carbon atoms of the substituent is not included in the number of carbon atoms.

[0031] The monovalent aromatic group which may have a substituent is preferably an aryl group which may have a substituent from the viewpoint of obtaining a cured product having a high glass transition temperature (Tg). The number of carbon atoms of the aryl group in R 1 and R 2 is preferably 6 to 20, more preferably 6 to 14, still more preferably 6 to 12. The number of carbon atoms of the substituent is not included in the number of carbon atoms. In a preferred embodiment, R1 and R 2 The monovalent aromatic group represented by is preferably a phenyl group which may have a substituent, a naphthyl group which may have a substituent, or a biphenyl group which may have a substituent, more preferably a phenyl group which may have a substituent or a naphthyl group which may have a substituent, and even more preferably a naphthyl group which may have a substituent.

[0032] In formula (A-1), X independently represents an oxygen atom or a sulfur atom, and preferably represents an oxygen atom. The compound of the present invention preferably has a furan skeleton having a carbonyl group bonded to the 2-position and 5-position, or a thiophene skeleton having a carbonyl group bonded to the 2-position and 5-position.

[0033] In formula (A-1), A independently represents one or more groups selected from the group represented by formula (A-2) and formula (A-3).

[0034] In formula (A-2), R 11 , and R 12 each independently represent a divalent aromatic group which may have a substituent. The divalent aromatic group refers to a group obtained by removing two hydrogen atoms from the aromatic ring of an aromatic compound. Examples of the divalent aromatic group which may have a substituent include an arylene group which may have a substituent and a heteroarylene group which may have a substituent. The number of carbon atoms of the divalent aromatic group is preferably 3 or more, more preferably 4 or more or 5 or more, even more preferably 6 or more, and the upper limit thereof is preferably 30 or less, more preferably 24 or less, even more preferably 18 or less or 14 or less, and particularly preferably 10 or less. The number of carbon atoms of the substituent is not included in the number of carbon atoms. In a preferred embodiment, R 11 , and R 12The divalent aromatic group represented by is a phenylene group which may have a substituent; a naphthylene group which may have a substituent; a phenylene group-fluorenylidene group-phenylene group which may have a substituent; a biphenylene group which may have a substituent; and more preferably, a phenylene group which may have a substituent or a naphthylene group which may have a substituent, and a phenylene group which may have a substituent is particularly preferred. When the divalent aromatic group has a substituent, the substituent is preferably an alkyl group, an alkenyl group or a hydroxy group, and more preferably a methyl group, an allyl group or a hydroxy group.

[0035] In formula (A-2), L 11 each independently represents a single bond or a divalent linking group which may have a substituent. Examples of the divalent linking group which may have a substituent include divalent organic groups composed of one or more (for example, 1 to 3000, 1 to 1000, 1 to 100, 1 to 50) skeletal atoms selected from a carbon atom, an oxygen atom, a nitrogen atom, and a sulfur atom, and an oxygen atom, a carbonyl group, a sulfonyl group, a divalent aliphatic group which may have a substituent, or a divalent aromatic group which may have a substituent are preferred. In a preferred embodiment, L 11 is a single bond, a divalent aliphatic group which may have a substituent, an oxygen atom, a divalent aromatic group which may have a substituent, a carbonyl group, or a sulfonyl group.

[0036] L 11 Examples of the divalent aliphatic group in include an alkylene group, a cycloalkylene group, an alkenylene group, a cycloalkenylene group, an alkapolyenylene group (the number of double bonds is preferably 2 to 10, more preferably 2 to 6, still more preferably 2 to 4, and even more preferably 2), etc., and an alkylene group, a cycloalkylene group, an alkenylene group, a cycloalkenylene group are preferred, an alkylene group, a cycloalkylene group are more preferred, and a cycloalkylene group is still more preferred.

[0037] L 11The alkylene group in [description] may be either linear or branched, and the number of its carbon atoms is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 4. The number of carbon atoms of the substituent is not included in the number of carbon atoms. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a 2-propylene group, a 1,1-dimethyl-3-methylpropylene group, a butylene group, a pentylene group, a hexylene group, and the like.

[0038] L 11 The number of carbon atoms of the cycloalkylene group in [description] is preferably 3 to 15, more preferably 3 to 12, and even more preferably 3 to 10. The number of carbon atoms of the substituent is not included in the number of carbon atoms. Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a decahydronaphthanylene group, a norbornanylene group, a dicyclopentanylene group, an adamantanylene group, and the like, and a dicyclopentanylene group is preferred.

[0039] L 11 The alkenylene group in [description] may be either linear or branched, and the number of its carbon atoms is preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4. The number of carbon atoms of the substituent is not included in the number of carbon atoms. Examples of the alkenylene group include an ethenylene group, a propenylene group, a butenylene group, a pentenylene group, a hexenylene group, and the like.

[0040] L 11 The number of carbon atoms of the cycloalkenylene group in [description] is preferably 3 to 15, more preferably 3 to 12, and even more preferably 3 to 10. The number of carbon atoms of the substituent is not included in the number of carbon atoms. Examples of the cycloalkenylene group include a cyclopropenylene group, a cyclobutenylene group, a cyclopentenylene group, a cyclohexenylene group, a norbornenylene group, and the like.

[0041] L 11 Examples of the divalent aromatic group in [description] include an arylene group and a heteroarylene group, and an arylene group is preferred.

[0042] L 11 In the arylene group, the number of carbon atoms is preferably 6 to 24, more preferably 6 to 18, and still more preferably 6 to 14. The number of carbon atoms of the substituent is not included in the number of carbon atoms. Examples of the arylene group include a phenylene group, a naphthylene group, an anthracenylene group, a fluorenediyl group (e.g., 9H-fluorene-9,9-diyl group), a fluorenylidene group, a phenanthrenediyl group, an indandiy group, a pyrenediyl group, etc. A phenylene group and a fluorenylidene group are preferable.

[0043] L 11 In the heteroarylene group, the number of carbon atoms is preferably 3 to 21, more preferably 3 to 15, and still more preferably 3 to 9. The number of carbon atoms of the substituent is not included in the number of carbon atoms. Examples of the heteroarylene group include a pyrrolediyl group, a furandiyl group, a thiophenediyl group, a pyridinediyl group, a pyridazinediyl group, a pyrimidinediyl group, a pyrazinediyl group, a triazinediyl group, a piperidinediyl group, a triazolediyl group, a purinediyl group, a carbazolediyl group, a quinolinediyl group, an isoquinolinediyl group, etc.

[0044] R 11 and L 11 may combine together to form a ring. In this case, L 11 is preferably a divalent aliphatic group which may have a substituent, and more preferably an alkylene group which may have a substituent. When a in formula (A-2) is 1, R 11 and L 11 preferably combine together to form a ring. Note that when R 11 and L 11 combine together to form a ring, it is preferable that a phenylene group and a cyclopentylene group are bonded to form an indane ring.

[0045] L 11From the viewpoint of providing a cured product having a high glass transition temperature (Tg), each independently, a single bond, a divalent aliphatic group which may have a substituent, an oxygen atom, a divalent aromatic group which may have a substituent, a carbonyl group, and a sulfonyl group are preferably represented. Each independently, a single bond, a divalent aliphatic group which may have a substituent, an oxygen atom, a phenylene group, a fluorenylidene group, a carbonyl group, or a sulfonyl group is more preferably represented. A single bond, an oxygen atom, a carbonyl group, a sulfonyl group, an alkylene group having 1 to 12 carbon atoms which may have a substituent, a cycloalkylene group having 3 to 15 carbon atoms which may have a substituent, or an arylene group having 6 to 24 carbon atoms which may have a substituent is preferred, and a cycloalkylene group having 3 to 15 carbon atoms which may have a substituent is more preferred.

[0046] In formula (A-2), a represents a number in the range of 0 to 5, preferably 0 to 4, more preferably 0 to 3, or 0 to 2. When a is 1, R 11 and L 11 may be bonded together to form a ring.

[0047] In formula (A-3), R 13 , and R 14 each independently represent a divalent aromatic group which may have a substituent. The divalent aromatic group is the same as the divalent aromatic group represented by R 11 in formula (A-2). In a preferred embodiment, the divalent aromatic group represented by R 13 , and R 14 is a phenylene group which may have a substituent or a naphthylene group which may have a substituent, and more preferably a phenylene group which may have a substituent. When the divalent aromatic group has a substituent, an alkyl group is preferred as the substituent, and a methyl group is more preferred.

[0048] In formula (A-3), L 12 represents a group represented by formula (A-4).

[0049] In formula (A-4), R 15 , and R16 each independently represents a divalent aromatic group which may have a substituent. The divalent aromatic group is the same as the divalent aromatic group represented by R in formula (A-2). 11 In a preferred embodiment, the divalent aromatic group represented by R 15 , and the divalent aromatic group represented by R 16 are each independently a phenylene group which may have a substituent or a naphthylene group which may have a substituent, more preferably a phenylene group which may have a substituent. When the divalent aromatic group has a substituent, the substituent is preferably an alkyl group, more preferably a methyl group.

[0050] In formula (A-4), L 13 each independently represents a single bond or a divalent linking group which may have a substituent. The divalent linking group is the same as the divalent linking group represented by L in formula (A-2). In a preferred embodiment, the divalent linking group represented by L 11 is an alkylene group having 1 to 12 carbon atoms which may have a substituent. 13

[0051] In formula (A-4), d represents a number in the range of 0 to 5, which is the same as the number in the range of 0 to 5 represented by a in formula (A-2). R 15 and L 13 may combine together to form a ring, and particularly when d is 1, it is preferable to form a ring.

[0052] In formula (A-3), b and c each independently represent a number in the range of 0 to 5, preferably a number in the range of 0 to 4, more preferably a number in the range of 0 to 3, or 0 to 2.

[0053] ​Among them, examples of A in formula (A-1) include groups represented by the following formulas (1a) to (13a). Among them, as A in formula (A-1), one or more groups selected from the groups represented by formulas (1a) to (4a) are preferable. In the formulas, a1 represents a number in the range of 0 to 4, b1 and c1 each independently represent a number in the range of 0 to 5, and "*" represents a bond. a1 is a value obtained by subtracting 1 from a in formula (A-2), and b1 and c1 are the same as b and c in formula (A-3). Further, in the group represented by formula (13a), d and e each represent an integer in the range of 0 to 4, and satisfy 1 ≤ d + e ≤ 4.

Chemical formula

[0054] In formula (A-1), n represents the number of repetitions and satisfies 0 ≤ n ≤ 8. The n is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, and preferably 7 or less, more preferably 6 or less, still more preferably 5 or less.

[0055] As a preferred embodiment of the compound of the present invention, In formula (A-1), R 1 and R 2 are each independently a phenyl group which may have a substituent, a naphthyl group which may have a substituent, or a biphenyl group which may have a substituent. In formula (A-1), X represents an oxygen atom or a sulfur atom. In formula (A-1), A each independently represents a group represented by formula (A-2) or formula (A-3). In formula (A-2), R 11 and R 12 are each independently a phenylene group which may have a substituent, a naphthylene group which may have a substituent, or a biphenylene group which may have a substituent. In formula (A-2), L 11 each independently represents a single bond, an oxygen atom, a carbonyl group, a sulfonyl group, a divalent aliphatic group which may have a substituent, or a divalent aromatic group which may have a substituent. In formula (A-2), a represents a number in the range of 0 to 5. When a is 1, R 11 and L 11 may combine together to form a ring. In formula (A-3), R 13 , and R 14 are each a phenylene group which may have a substituent, L 12 is a group represented by formula (A-4), In formula (A-4), R 15 , and R 16 are each a phenylene group which may have a substituent, In formula (A-4), L 13 is a divalent aliphatic group which may have a substituent, In formula (A-4), d represents a number in the range of 0 to 5, In formula (A-3), a and b each independently represent a number in the range of 0 to 5. In formula (A-1), n represents the number of repetitions and satisfies 0 ≤ n ≤ 8.

[0056] Specific examples of the compounds of the present invention include the following compounds (1) to (18). However, the compounds are not limited to these specific examples. In the formula, n is 0 ≤ n ≤ 8, a, b, and c each represent a number in the range of 0 to 5. d and e each represent an integer in the range of 0 to 4, and satisfy 1 ≤ d + e ≤ 4.

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0057] From the perspective of obtaining a cured product with a high glass transition temperature (Tg), the number average molecular weight (Mn) of the compound of the present invention is preferably 5000 or less, more preferably 4000 or less, still more preferably 3000 or less, and is preferably 100 or more, more preferably 500 or more, still more preferably 1000 or more. The number average molecular weight can be measured as a value in terms of polystyrene by gel permeation chromatography (GPC) method.

[0058] From the perspective of obtaining a cured product with a high glass transition temperature (Tg), the molecular weight distribution (Mw / Mn) of the compound of the present invention is preferably 2 or less, more preferably 1.8 or less, still more preferably 1.5 or less, and is preferably 0.5 or more, more preferably 0.7 or more, still more preferably 1.0 or more.

[0059] From the perspective of obtaining a cured product with a high glass transition temperature (Tg), the active group equivalent (active ester group equivalent) of the compound of the present invention is preferably 100 g / eq. or more, more preferably 120 g / eq. or more, still more preferably 130 g / eq. or more, and is preferably 1000 g / eq. or less, more preferably 750 g / eq. or less, still more preferably 300 g / eq. or less. The active group equivalent is the mass of the compound of the present invention containing 1 equivalent of the active group.

[0060] From the perspectives of energy conservation, cost reduction, and environmental protection, the compound of the present invention is preferably synthesized using plant-derived raw materials. For example, a compound having a furan ring can be derived from biomass such as plant-derived glucose, plant-derived cellulose, and plant-derived fructose. Such a compound having a furan ring derived from biomass is, for example, a compound in which a carbonyl group is bonded to the 2-position and 5-position of the furan skeleton, and specifically, 2,5-furandicarboxylic acid, etc. Therefore, when the compound of the present invention is synthesized using a compound having a furan ring derived from biomass as a raw material and the compound of the present invention has the skeleton of a compound having a furan ring derived from biomass, the compound of the present invention is in an embodiment in which X in formula (A-1) is an oxygen atom and a furan skeleton having carbonyl groups bonded to the 2-position and 5-position.

[0061] From the viewpoint of reducing the environmental load, the biomass ratio of the compound of the present invention is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more. The upper limit is not particularly limited, but is preferably 100% by mass or less, more preferably 75% by mass or less, still more preferably 50% by mass or less, 30% by mass or less, 10% by mass or less. The biomass ratio is the ratio of the biomass-derived components contained in the compound, and specifically can be measured by the method described in the examples below. Even when the compound of the present invention is a compound that has received certification by the mass balance method, the biomass ratio of the compound of the present invention is calculated by the method described in the examples below.

[0062] The compound of the present invention 1) A hydroxy group-containing aromatic compound having an aromatic hydroxy group, 2) A dicarboxylic acid halide having a furan skeleton or a thiophene skeleton, and 3) A divalent phenol compound can be obtained by subjecting them to a condensation reaction.

[0063] The hydroxy group-containing aromatic compound is a compound in which a hydroxy group is bonded to a monovalent aromatic group, and the aromatic group of the compound can constitute R 1 and R 2 in formula (A-1). Examples of such compounds include 1-naphthol, phenol, orthophenylphenol, isobornylphenol, cardanol, eugenol, and the like.

[0064] The dicarboxylic acid halide having a furan skeleton or a thiophene skeleton is a compound in which two carbonyl halides are bonded to a furan skeleton or a thiophene skeleton. Examples of such compounds include 2,5-furandicarboxylic acid chloride, 2,5-thiophenedicarboxylic acid chloride, and the like. When a compound having a biomass-derived furan ring is used, the compound having a biomass-derived furan ring may be chlorinated and then used as a raw material for the compound of the present invention.

[0065] The divalent phenol compound is a compound in which a dicarboxylic acid halide having a furan skeleton or a thiophene skeleton reacts with the phenol moiety of the compound, and can constitute A in formula (A-1). Examples of such compounds include dicyclopentadiene-phenol adduct, 4,4'-(9-fluorenylidene)diphenol, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxybenzophenone, bisphenol A, bisphenol F, 2,2'-diallylbisphenol A, bisphenol S, 4,4'-dihydroxybiphenyl, 2,7-naphthalenediol, daidzein, etc. Also, a commercially available divalent phenol compound may be used. Examples of commercially available products include "J-DPP85" manufactured by JFE Chemical Corporation, "SA90" manufactured by SABIC Innovative Plastics, etc.

[0066] In the condensation reaction, a phase transfer catalyst such as tetra-n-butylammonium bromide may be used as necessary. The phase transfer catalyst etc. may be any conventionally known one that can be used in the esterification reaction. Also, in the condensation reaction, a base may be used. Examples of the base include alkali metal hydroxides such as sodium hydroxide (caustic soda) and potassium hydroxide; tertiary amines such as triethylamine, pyridine, N,N-diisopropylethylamine, etc. The base may be used alone or in combination of two or more.

[0067] In addition, the condensation reaction may proceed in a solvent-free system without using a solvent, or may proceed in an organic solvent system using an organic solvent. Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; acetate solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitol solvents such as cellosolve and butyl carbitol; aromatic hydrocarbon solvents such as toluene and xylene; and amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone. The organic solvent may be used alone or in combination of two or more.

[0068] The reaction temperature may be, for example, in the range of 0 to 80°C. The reaction time may be, for example, in the range of 30 minutes to 8 hours.

[0069] After completion of the reaction, if necessary, in order to remove by-product salts and excess starting materials from the system, purification steps such as washing with water and microfiltration may be performed. Specifically, after adding an amount of water necessary to dissolve the by-product salts and stirring, the aqueous layer is discarded. Thereafter, the organic layer is dried, and if necessary, the organic solvent is distilled off to obtain the compound of the present invention. The organic solvent may be used as it is without being completely removed as the solvent of the resin composition.

[0070] [Resin Composition] The resin composition of the present invention contains (A) the compound of the present invention, (B) a thermosetting resin, and (C) an inorganic filler. According to such a resin composition, it is possible to obtain a cured product having a high glass transition temperature. Further, usually, it is also possible to obtain a cured product having a high peel strength and a low dielectric tangent.

[0071] The resin composition may further contain (D) a radically polymerizable resin, (E) a curing accelerator, (F) an organic filler, (G) a thermoplastic resin, and (H) other additives in combination with (A) the compound of the present invention, (B) a thermosetting resin, and (C) an inorganic filler.

[0072] The resin composition contains, as component (A), the compound of the present invention. Component (A) has a function of forming a bond by reacting with a (B) thermosetting resin as an active ester resin (polyester resin) to cure the resin composition. The compound of the present invention contained in the resin composition is as described in the above [Compound] column.

[0073] When the number of epoxy groups of the epoxy resin as component (B) is taken as 1, the number of active groups of component (A) is preferably 0.01 or more, more preferably 0.05 or more, still more preferably 0.1 or more, and preferably 5 or less, more preferably 3 or less, still more preferably 1 or less, from the viewpoint of significantly obtaining the effects of the present invention. The "number of epoxy groups of the epoxy resin" represents the total value obtained by dividing the mass of the non-volatile component of the epoxy resin present in the resin composition by the epoxy equivalent. Further, the "number of active groups of component (A)" represents the total value obtained by dividing the mass of the non-volatile component of component (A) present in the resin composition by the active group equivalent.

[0074] When the non-volatile component of the resin composition is 100% by mass, the content of component (A) is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, from the viewpoint of significantly obtaining the effects of the present invention. In addition, the content of each component in the resin composition is a value when the non-volatile component in the resin composition is 100% by mass, unless otherwise specified, and the non-volatile component means the entire non-volatile component excluding the solvent in the resin composition.

[0075] <(B) thermosetting resin> The resin composition contains, as component (B), a (B) thermosetting resin. The type of the (B) thermosetting resin is not particularly limited as long as it can be cured in combination with component (A). The (B) thermosetting resin as component (B) does not include those corresponding to the above-mentioned component (A). The (B) thermosetting resin may be used alone or in combination of two or more.

[0076] Examples of the thermosetting resin include epoxy resins, phenolic resins, cyanate resins, active ester resins, carbodiimide resins, acid anhydride resins, amine resins, benzoxazine resins, and thiol resins. The thermosetting resin may be used alone or in combination of two or more. Among them, the thermosetting resin preferably contains at least one selected from the group consisting of epoxy resins, phenolic resins, and cyanate resins.

[0077] In particular, from the viewpoint of significantly obtaining the effects of the present invention, it is preferable to use a combination of an epoxy resin and a resin capable of reacting with the epoxy resin to cure the resin composition. A resin capable of reacting with the epoxy resin to cure the resin composition may hereinafter be referred to as a "curing agent". Examples of the curing agent include, for example, phenolic resins, cyanate resins, active ester resins, carbodiimide resins, acid anhydride resins, amine resins, benzoxazine resins, and thiol resins. Among them, the curing agent preferably contains at least one selected from the group consisting of phenolic resins and cyanate resins. The curing agent may be used alone or in combination of two or more.

[0078] Epoxy resin is a thermosetting resin having an epoxy group. Examples of epoxy resins include bisxylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, tris-phenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolak type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, isocyanurate type epoxy resin, phenolphthalimide type epoxy resin, and the like. The epoxy resin may be used alone or in combination of two or more.

[0079] (B) The thermosetting resin preferably contains, as the epoxy resin, an epoxy resin having two or more epoxy groups in one molecule. The ratio of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more based on 100% by mass of the non-volatile component of the epoxy resin.

[0080] Epoxy resins include epoxy resins that are liquid at 20°C (hereinafter sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid at 20°C (hereinafter sometimes referred to as "solid epoxy resins"). The resin composition may contain only a liquid epoxy resin, or only a solid epoxy resin, or a combination of a liquid epoxy resin and a solid epoxy resin as the epoxy resin.

[0081] As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferable.

[0082] As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, and epoxy resin having a butadiene structure are preferable, and bisphenol A type epoxy resin and naphthalene type epoxy resin are more preferable.

[0083] Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene-type epoxy resin) manufactured by DIC Corporation; "828US", "828EL", "jER828EL", "825", "Epicoat 828EL" (bisphenol A-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER807", "1750" (bisphenol F-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630", "630LSD", "604" (glycidylamine-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ED-523T" (glycerol-type epoxy resin) manufactured by ADEKA Corporation; "EP-3950L", "EP-3980S" (glycidylamine-type epoxy resin) manufactured by ADEKA Corporation; "EP-4088S" (dicyclopentadiene-type epoxy resin) manufactured by ADEKA Corporation; "ZX1059" (a mixture of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "EX-721" (glycidyl ester-type epoxy resin) manufactured by Nagase ChemteX Corporation; "Celloxide 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by Daicel Corporation; "PB-3600", "JP-100", "JP-200" (epoxy resin having a butadiene structure (epoxidized polybutadiene resin)) manufactured by Nippon Soda Co., Ltd.; "ZX1658", "ZX1658GS" (liquid 1,4-glycidylcyclohexane-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd., etc. These may be used alone or in combination of two or more.

[0084] As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferred, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferred.

[0085] Examples of the solid epoxy resin include a bicyclonol type epoxy resin, a naphthalene type epoxy resin, a naphthalene type tetrafunctional epoxy resin, a naphthol novolak type epoxy resin, a cresol novolak type epoxy resin, a dicyclopentadiene type epoxy resin, a trisphenol type epoxy resin, a naphthol type epoxy resin, a biphenyl type epoxy resin, a naphthylene ether type epoxy resin, an anthracene type epoxy resin, a bisphenol A type epoxy resin, a bisphenol AF type epoxy resin, a phenol aralkyl type epoxy resin, a tetraphenylethane type epoxy resin, and a phenolphthalimide type epoxy resin. Among them, a biphenyl type epoxy resin and a naphthylene ether type epoxy resin are preferred, and a biphenyl type epoxy resin and a naphthylene ether type epoxy resin are more preferred.

[0086] Specific examples of the solid epoxy resin include "HP4032H" (naphthalene-type epoxy resin) manufactured by DIC Corporation; "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resin) manufactured by DIC Corporation; "N-690" (cresol novolak-type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolak-type epoxy resin) manufactured by DIC Corporation; "HP-7200", "HP-7200HH", "HP-7200H", and "HP-7200L" (dicyclopentadiene-type epoxy resin) manufactured by DIC Corporation; "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", and "HP6000" (naphthylene ether-type epoxy resin) manufactured by DIC Corporation; "EPPN-502H" (trisphenol-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC7000L" (naphthol novolak-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC3000H", "NC3000", "NC3000L", "NC3000FH", and "NC3100" (biphenyl-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "ESN475V" and "ESN4100V" (naphthalene-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "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", and "YL7890" (bixylenol-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL6121" (biphenyl-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX7700" (phenol aralkyl-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd.; "YX7760" (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; "WHR991S" (phenolphthalimide-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., and the like.These may be used alone or in combination of two or more kinds.

[0087] When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, their mass ratio (liquid epoxy resin:solid epoxy resin) is preferably 1:0.01 to 1:20, more preferably 1:0.05 to 1:10, and particularly preferably 1:0.1 to 1:7.

[0088] The epoxy equivalent of the epoxy resin is preferably 50 g / eq. to 5,000 g / eq., more preferably 60 g / eq. to 3,000 g / eq., still more preferably 80 g / eq. to 2,000 g / eq., and particularly preferably 110 g / eq. to 1,000 g / eq. The epoxy equivalent represents the mass of the resin per equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

[0089] The weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, and still more preferably 400 to 1,500. The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by gel permeation chromatography (GPC) method.

[0090] From the viewpoint of obtaining a cured product showing good mechanical strength and insulation reliability, when the non-volatile components in the resin composition are taken as 100% by mass, the content of the epoxy resin as the component (B) is preferably 1% by mass or more, more preferably 5% by mass or more, and particularly preferably 10% by mass or more, and is preferably 45% by mass or less, more preferably 40% by mass or less, and particularly preferably 20% by mass or less.

[0091] As the phenolic resin, a compound having one or more, preferably two or more hydroxyl groups bonded to an aromatic ring such as a benzene ring or a naphthalene ring in one molecule can be used. Since the phenolic resin can react with the epoxy resin to cure the resin composition when combined with the epoxy resin, it is sometimes referred to as a "phenolic curing agent". From the viewpoint of significantly obtaining the effects of the present invention, a phenolic resin having a novolak structure is preferred. Also, from the viewpoint of adhesion, a nitrogen-containing phenolic resin is preferred, and a phenolic resin containing a triazine skeleton is more preferred. Among them, from the viewpoint of significantly obtaining the effects of the present invention, a phenolic novolak resin containing a triazine skeleton is preferred. Specific examples of the phenolic resin include, for example, "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., "NHN", "CBN", "GPH" manufactured by Nippon Kayaku Co., Ltd., "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-375", "SN-395" manufactured by Nippon Steel Chemical & Material Co., Ltd., "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P", "LA-1356", "TD2090", "TD-2090-60M", "KA-1163" manufactured by DIC Corporation, etc.

[0092] As the cyanate resin, a compound having one or more, preferably two or more cyanate groups in one molecule can be used. Since the cyanate resin can react with an epoxy resin to cure the resin composition when combined with the epoxy resin, it is sometimes referred to as a "cyanate-based curing agent". Examples of the cyanate resin 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'-ethylidenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanatephenyl)thioether, and bis(4-cyanatephenyl)ether; polyfunctional cyanate resins derived from phenol novolak and cresol novolak; prepolymers in which some of these cyanate resins are partially triazine-ized; and the like. Specific examples of the cyanate resin include "PT30" and "PT60" (both are phenol novolak type polyfunctional cyanate resins), "BA230", "BA230S75" (a prepolymer in which part or all of bisphenol A dicyanate is triazine-ized to form a trimer), etc. manufactured by Lonza Japan Co., Ltd.

[0093] As the active ester resin, generally, compounds having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, etc., are preferably used. Since the active ester resin can react with the epoxy resin to cure the resin composition when combined with the epoxy resin, it is sometimes referred to as an "active ester-based curing agent". The active ester resin is preferably obtained by a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. Particularly from the viewpoint of improving the high-temperature reflow swelling resistance, an active ester resin obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester resin obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, etc. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-type diphenol compounds, phenol novolac, etc. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

[0094] Specifically, as the active ester resin, a dicyclopentadiene type active ester resin, a naphthalene type active ester resin containing a naphthalene structure, an active ester resin containing an acetylated product of phenol novolak, and an active ester resin containing a benzoylated product of phenol novolak are preferable. Among them, at least one selected from a dicyclopentadiene type active ester resin and a naphthalene type active ester resin is more preferable. As the dicyclopentadiene type active ester resin, an active ester resin containing a dicyclopentadiene type diphenol structure is preferable.

[0095] Examples of commercially available active ester resins include, for example, as an active ester resin containing a dicyclopentadiene type diphenol structure, "EXB9451", "EXB9460", "EXB9460S", "EXB-8000L", "EXB-8000L-65M", "EXB-8000L-65TM", "HPC-8000L-65TM", "HPC-8000L-65T", "HPC-8000", "HPC-8000-65T", "HPC-8000H", "HPC-8000H-65TM" (manufactured by DIC Corporation); as an active ester resin containing a naphthalene structure, "HP-B-8151-62T", "EXB-8100L-65T", "EXB-8150-60T", "EXB-8150-62T", "EXB-9416-70BK", "HPC-8150-60T", "HPC-8150-62T", "EXB-8" (manufactured by DIC Corporation); as a phosphorus-containing active ester resin, "EXB9401" (manufactured by DIC Corporation); as an active ester resin which is an acetylated product of phenol novolak, "DC808" (manufactured by Mitsubishi Chemical Corporation); as an active ester resin which is a benzoylated product of phenol novolak, "YLH1026", "YLH1030", "YLH1048" (manufactured by Mitsubishi Chemical Corporation); and as an active ester resin containing a styryl group and a naphthalene structure, "PC1300-02-65MA" (manufactured by Air Water Inc.), etc.

[0096] As the carbodiimide resin, a compound having one or more, preferably two or more carbodiimide structures in one molecule can be used. Since the carbodiimide resin can react with an epoxy resin to cure the resin composition when combined with the epoxy resin, it is sometimes referred to as a "carbodiimide-based curing agent". Specific examples of the carbodiimide resin include aliphatic biscarbodiimides such as tetramethylene-bis(t-butylcarbodiimide) and cyclohexane bis(methylene-t-butylcarbodiimide); biscarbodiimides such as aromatic biscarbodiimides like phenylene-bis(xilylcarbodiimide); aliphatic polycarbodiimides such as polyhexamethylene carbodiimide, polytrimethylhexamethylene carbodiimide, polycyclohexylene carbodiimide, poly(methylenebiscyclohexylene carbodiimide), and poly(isophorone carbodiimide); aromatic polycarbodiimides such as poly(phenylene carbodiimide), poly(naphthylene carbodiimide), poly(tolylene carbodiimide), poly(methyldiisopropylphenylene carbodiimide), poly(triethylphenylene carbodiimide), poly(diethylphenylene carbodiimide), poly(triisopropylphenylene carbodiimide), poly(diisopropylphenylene carbodiimide), poly(xylene carbodiimide), poly(tetramethylxylene carbodiimide), poly(methylenediphenylene carbodiimide), and poly[methylenebis(methylphenylene) carbodiimide], etc. Examples of commercially available carbodiimide resins include, for example, "Carbodilite V-02B", "Carbodilite V-03", "Carbodilite V-04K", "Carbodilite V-07", and "Carbodilite V-09" manufactured by Nisshinbo Chemical Co., Ltd.; "Stabaxol P", "Stabaxol P400", "Highcadil 510", etc. manufactured by Rhein Chemie Co., Ltd.

[0097] As the acid anhydride resin, a compound having one or more, preferably two or more acid anhydride groups in one molecule can be used. Since the acid anhydride resin can react with an epoxy resin to cure the resin composition when combined with an epoxy group, it is sometimes referred to as an "acid anhydride-based curing agent". Specific examples of the acid anhydride resin include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl nadic anhydride, hydrogenated methyl nadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, ethylene glycol bis(anhydrotrimellitate), and polymer-type acid anhydrides such as a styrene-maleic acid resin copolymerized from styrene and maleic acid. Commercially available products of the acid anhydride resin include, for example, "HNA-100", "MH-700", "MTA-15", "DDSA", "OSA" manufactured by Shin Nippon Rika Co., Ltd.; "YH-306", "YH-307" manufactured by Mitsubishi Chemical Corporation; "HN-2200", "MHAC-P" manufactured by Resonaak Co., Ltd.; "EF-30", "EF-40", "EF-60", "EF-80", etc. manufactured by Cray Valley Co., Ltd.

[0098] As the amine resin, a compound having one or more, preferably two or more amino groups in one molecule can be used. Since the amine resin can react with an epoxy resin to cure the resin composition when combined with an epoxy group, it is sometimes referred to as an "amine-based curing agent". Examples of the amine resin include aliphatic amines, polyether amines, alicyclic amines, aromatic amines, etc. Among them, aromatic amines are preferred. The amine resin is preferably a primary amine or a secondary amine, and more preferably a primary amine. Specific examples of the amine resin include 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, etc. Commercially available products of the amine resin include, for example, "SEIKACURE-S" manufactured by Seika Corporation; "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD A-A", "KAYAHARD A-B", "KAYAHARD A-S" manufactured by Nippon Kayaku Co., Ltd.; "EPICURE W" manufactured by Mitsubishi Chemical Corporation; "DTDA" manufactured by Sumitomo Seika Chemicals Co., Ltd., etc.

[0099] Since benzoxazine resin can react with epoxy resin to cure the resin composition when combined with epoxy resin, it is sometimes referred to as a "benzoxazine-based curing agent". Specific examples of benzoxazine resin include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Corporation; "HFB2006M" manufactured by Showa Highpolymer Co., Ltd.; "P-d" and "F-a" manufactured by Shikoku Kasei Kogyo Co., Ltd., etc.

[0100] Since thiol resin can react with epoxy resin to cure the resin composition when combined with epoxy resin, it is sometimes referred to as a "thiol-based curing agent". Examples of thiol resin include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), tris(3-mercaptopropyl) isocyanurate, etc.

[0101] The active group equivalent weight of the curing agent is preferably 50 g / eq. to 3000 g / eq., more preferably 100 g / eq. to 1000 g / eq., still more preferably 100 g / eq. to 500 g / eq., and particularly preferably 100 g / eq. to 300 g / eq. The active group equivalent weight is the mass of the curing agent per equivalent of the active group.

[0102] The weight average molecular weight (Mw) of the curing agent is preferably 100 to 5,000, more preferably 250 to 3,000, and still more preferably 400 to 1,500. The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by the gel permeation chromatography (GPC) method.

[0103] When the epoxy equivalent of the epoxy resin is set to 1, the active equivalent of the curing agent is preferably 0.01 or more, more preferably 0.05 or more, still more preferably 0.1 or more, and preferably 5 or less, more preferably 3 or less, particularly preferably 2 or less. The "epoxy equivalent of the epoxy resin" represents the total value obtained by summing up the values obtained by dividing the mass of the non-volatile component of the epoxy resin present in the resin composition by the epoxy equivalent. Further, the "active equivalent of the curing agent" represents the total value obtained by summing up the values obtained by dividing the mass of the non-volatile component of the curing agent present in the resin composition by the active equivalent.

[0104] (B) From the viewpoint of significantly obtaining the effects of the present invention, when the non-volatile components in the resin composition are 100% by mass, the content of the curing agent as the component (B) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, still more preferably 0.5% by mass or more, and preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, 5% by mass or less, 3% by mass or less.

[0105] (B) From the viewpoint of significantly obtaining the effects of the present invention, when the non-volatile components in the resin composition are 100% by mass, the content of the thermosetting resin is preferably 10.1% by mass or more, more preferably 10.3% by mass or more, still more preferably 10.5% by mass or more, and preferably 65% by mass or less, more preferably 60% by mass or less, still more preferably 55% by mass or less, 50% by mass or less, 48% by mass or less.

[0106] <(C) Inorganic filler> The resin composition contains (C) an inorganic filler as the component (C). By including the component (C) in the resin composition, the dielectric tangent of the cured product can be reduced.

[0107] (C) As the material of the inorganic filler, an inorganic compound is used. (C) As the material of the inorganic filler, for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate, etc. may be mentioned. Among these, silica is particularly preferable. As silica, for example, amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, etc. may be mentioned. Also, spherical silica is preferable as silica. (C) The inorganic filler may be used alone or in combination of two or more kinds in any ratio.

[0108] (C) Examples of commercially available products of the inorganic filler include "SP60-05", "SP507-05" manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", "YA010C", "SC2500SQ", "SO-C4", "SO-C2", "SO-C1" manufactured by Admatechs Co., Ltd.; "UFP-30", "DAW-03", "FB-105FD" manufactured by Denka Co., Ltd.; "Silfill NSS-3N", "Silfill NSS-4N", "Silfill NSS-5N" manufactured by Tokuyama Corporation; "Selfiers", "MGH-005" manufactured by Taiheiyo Cement Corporation; "Esferic", "BA-1" manufactured by JGC Catalysts & Chemicals Ltd., etc.

[0109] (C) The inorganic filler may be an inorganic filler derived from biomass. The inorganic filler derived from biomass is preferably produced from plant raw materials. For example, plants of the families Toxaceae and Poaceae have the property of absorbing and accumulating silicon components from the ground. Therefore, by burning these plants, silica can be produced as combustion ash (Japanese Patent No. 6389349). Commercial products may be used as the inorganic filler derived from biomass. Examples of commercial products of the inorganic filler derived from biomass include "Ethical Silica" manufactured by M.I.T. as biomass silica produced from rice husks.

[0110] (C) 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, still more preferably 3 μm or less, even more preferably 2 μm or less, and particularly preferably 1.5 μm or less. The lower limit of the average particle size of the (C) inorganic filler is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, still more preferably 0.1 μm or more, and particularly preferably 0.2 μm or more. The average particle size of the (C) inorganic filler can be measured by the laser diffraction / scattering method based on the Mie scattering theory. Specifically, it can be measured by creating a volume-based particle size distribution of the inorganic filler with a laser diffraction scattering type particle size distribution measuring device and taking the median diameter thereof as the average particle size. As the measurement sample, 100 mg of the inorganic filler and 10 g of methyl ethyl ketone can be weighed into a vial and dispersed by ultrasonic waves for 10 minutes. The measurement sample can be used to measure the volume-based particle size distribution of the inorganic filler in a flow cell method using a laser diffraction type particle size distribution measuring device with the wavelengths of the light sources used being blue and red, and the average particle size can be calculated as the median diameter from the obtained particle size distribution. Examples of the laser diffraction type particle size distribution measuring device include "LA-960" manufactured by Horiba, Ltd.

[0111] (C) The specific surface area of the inorganic filler is not particularly limited, but is preferably 0.1 m 2 / g or more, more preferably 0.5 m 2 / g or more, still more preferably 1 m 23 m / g or more, particularly preferably 3 m / g or more. 2 Although the upper limit of the specific surface area of the inorganic filler is not particularly limited, it is preferably 100 m 2 / g or less, more preferably 70 m 2 / g or less, still more preferably 50 m 2 / g or less, even more preferably 30 m 2 / g or less, particularly preferably 10 m 2 / g or less. The specific surface area of the inorganic filler can be obtained by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) in accordance with the BET method and calculating the specific surface area using the BET multi-point method.

[0112] (C) From the viewpoint of enhancing moisture resistance and dispersibility, the inorganic filler is preferably treated with a surface treatment agent. Examples of the surface treatment agent include fluorine-containing silane coupling agents, aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, silane-based coupling agents, alkoxysilanes, organosilazane compounds, titanate-based coupling agents, and the like. Further, the surface treatment agent may be used alone or in any combination of two or more.

[0113] Examples of commercially available surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-4803" (long-chain epoxy type silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

[0114] From the perspective of improving the dispersibility of the inorganic filler, the degree of surface treatment with the surface treatment agent preferably falls within a predetermined range. 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, more preferably surface-treated with 0.2% to 3% by mass, and even more preferably surface-treated with 0.3% to 2% by mass.

[0115] 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 perspective of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg / m 2 or more, more preferably 0.1 mg / m 2 or more, and even more preferably 0.2 mg / m 2 or more. On the other hand, from the perspective of preventing an increase in the melt viscosity of the resin composition and the melt viscosity in the sheet form, it is preferably 1.0 mg / m 2 or less, more preferably 0.8 mg / m 2 or less, and even more preferably 0.5 mg / m 2 or less.

[0116] (C) The amount of carbon per unit surface area of the inorganic filler can be measured after washing the surface-treated inorganic filler with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with the 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, "EMIA-320V" manufactured by Horiba, Ltd. etc. can be used.

[0117] (C) From the perspective of obtaining a cured product with a low dielectric tangent, when the non-volatile components in the resin composition are 100% by mass, the content of the inorganic filler is preferably 30% by mass or more, more preferably 60% by mass or more, even more preferably 65% by mass or more, preferably 85% by mass or less, more preferably 80% by mass or less, and even more preferably 75% by mass or less.

[0118] <(D) Radical polymerizable resin> The resin composition may further contain, as an optional component, a (D) radical polymerizable resin in combination with the above-described components (A) to (C). The (D) radical polymerizable resin as this (D) component does not include those corresponding to the above-described components (A) to (C).

[0119] The type of the radical polymerizable resin is not particularly limited as long as it has one or more (preferably two or more) radical polymerizable unsaturated groups in one molecule. Examples of the radical polymerizable resin include resins having, as the radical polymerizable unsaturated group, one or more selected from a maleimide group, a vinyl group, an allyl group, a styryl group, a vinylphenyl group, an acryloyl group, a methacryloyl group, a propenyl group, a fumaroyl group, and a maleoyl group. Among them, from the viewpoint of significantly obtaining the effects of the present invention, the radical polymerizable resin is preferably one or more selected from a maleimide resin, a (meth)acrylic resin, and a styryl resin, and more preferably a maleimide resin.

[0120] The type of the maleimide resin is not particularly limited as long as it has one or more (preferably two or more) maleimide groups (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl groups) in one molecule. Examples of the maleimide resin include (1) maleimide resins containing an aliphatic skeleton (preferably an aliphatic skeleton having 36 carbon atoms derived from dimer diamine) such as "BMI-3000J", "BMI-5000", "BMI-1400", "BMI-1500", "BMI-1700", "BMI-689" (all manufactured by Dicna Moleculars), "SLK6895-T90" (manufactured by Shin-Etsu Chemical Co., Ltd.); (2) maleimide resins containing an indane skeleton described in JP-A No. 2020-500211 of the Japan Institute of Invention and Innovation; and (3) maleimide resins containing an aromatic ring skeleton directly bonded to the nitrogen atom of the maleimide group such as "MIR-3000-70MT" (manufactured by Nippon Kayaku Co., Ltd.), "BMI-4000" (manufactured by Daiwa Kasei Co., Ltd.), and "BMI-80" (manufactured by KAI Chemical Co., Ltd.).

[0121] (Meta)acrylic resins are not particularly limited in type as long as they have one or more (preferably two or more) (meta)acryloyl groups in one molecule, and may be monomers or oligomers. Here, the term "(meta)acryloyl group" is a general term for acryloyl groups and methacryloyl groups. Examples of methacrylic resins include, in addition to (meta)acrylate monomers, (meta)acrylic resins such as "A-DOG" (manufactured by Shin-Nakamura Chemical Co., Ltd.), "DCP-A" (manufactured by Kyoeisha Chemical Co., Ltd.), "NPDGA", "FM-400", "R-687", "THE-330", "PET-30", and "DPHA" (all manufactured by Nippon Kayaku Co., Ltd.).

[0122] Styryl resins are not particularly limited in type as long as they have one or more (preferably two or more) styryl groups or vinylphenyl groups in one molecule, and may be monomers or oligomers. Examples of styryl resins include, in addition to styrene monomers, styryl resins such as "OPE-2St", "OPE-2St 1200", and "OPE-2St 2200" (all manufactured by Mitsubishi Gas Chemical Company, Inc.).

[0123] From the viewpoint of significantly obtaining the effects of the present invention, when the non-volatile components in the resin composition are 100% by mass, the content of component (D) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, still more preferably 0.5% by mass or more, preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably 2% by mass or less.

[0124] <(E) Curing accelerator> The resin composition may further contain an (E) curing accelerator as an optional component in combination with the above-described components (A) to (C). The (E) curing accelerator as component (E) does not include those corresponding to the above-described components (A) to (D). The (E) curing accelerator has a function as a curing catalyst that accelerates the curing of the epoxy resin in the (B) thermosetting resin.

[0125] (E) As a curing accelerator, a compound that accelerates the curing of the epoxy resin can be used. Examples of such (E) curing accelerators include phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, amine-based curing accelerators, and the like. The (E) curing accelerator may be used alone or in combination of two or more kinds.

[0126] Examples of phosphorus-based hardening accelerators include aliphatic phosphonium salts such as tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium) pyromellitate, tetrabutylphosphonium hydrogen hexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, di-tert-butyldimethylphosphonium tetraphenylborate; aromatic phosphonium salts such as methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate; aromatic phosphine-borane complexes such as triphenylphosphine·triphenylborane; aromatic phosphine-quinone addition reactants such as triphenylphosphine·p-benzoquinone addition reactant; aliphatic phosphines such as tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl(2-butenyl)phosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, tricyclohexylphosphine;Aromatic phosphines such as 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, 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, 2,2'-bis(diphenylphosphino)diphenylether, etc. are mentioned.;

[0127] Examples of urea-based curing accelerators include, for example, 1,1-dimethylurea; aliphatic dimethylureas such as 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, 3-cyclooctyl-1,1-dimethylurea; aromatic dimethylureas such as 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, 3-(3,4-dimethylphenyl)-1,1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N’,N’-dimethylurea), N,N-(4-methyl-1,3-phenylene)bis(N’,N’-dimethylurea) [toluene bisdimethylurea], and the like.

[0128] Examples of guanidine-based curing accelerators include, for example, 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, 1-(o-tolyl)biguanide, and the like.

[0129] Examples of imidazole-based curing accelerators include imidazole compounds such as 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, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-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, 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, 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins. Commercially available products of imidazole-based curing accelerators include, for example, "1B2PZ", "2E4MZ", "2MZA-PW", "2MZ-OK", "2MA-OK", "2MA-OK-PW", "2PHZ", "2PHZ-PW", "Cl1Z", "Cl1Z-CN", "Cl1Z-CNS", "C11Z-A" manufactured by Shikoku Kasei Kogyo Co., Ltd.; "P200-H50" manufactured by Mitsubishi Chemical Corporation, etc.

[0130] Examples of the metal-based hardening accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include organocobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate, organocopper complexes such as copper(II) acetylacetonate, 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 the organometallic salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0131] Examples of the amine-based hardening accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, and the like. As the amine-based hardening accelerator, commercially available products may be used, and examples thereof include "MY-25" manufactured by Ajinomoto Fine-Techno Co., Inc.

[0132] (E) From the viewpoint of significantly obtaining the effects of the present invention, when the non-volatile components in the resin composition are 100% by mass, the content of the hardening accelerator is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, still more preferably 0.03% by mass or more, and preferably 1% by mass or less, more preferably 0.5% by mass or less, still more preferably 0.1% by mass or less.

[0133] <(F) Organic filler> The resin composition may further contain (F) an organic filler as an optional component. The (F) organic filler as this (F) component does not include those corresponding to the above-described components (A) to (E). As the organic filler, any organic filler that can be used when forming the insulating layer of the printed wiring board may be used, and examples thereof include rubber particles, polyamide fine particles, and silicone particles.

[0134] As the rubber particles, commercially available products may be used. For example, "EXL2655" manufactured by Dow Chemical Japan, "AC3401N" and "AC3816N" manufactured by Aika Industries Co., Ltd., etc. may be mentioned.

[0135] (F) From the viewpoint of significantly obtaining the effects of the present invention, when the non-volatile components in the resin composition are 100% by mass, the content of the organic filler is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, still more preferably 0.5% by mass or more, and preferably 3% by mass or less, more preferably 2% by mass or less, still more preferably 1.5% by mass or less.

[0136] <(G) Thermoplastic resin> The resin composition of the present invention may further contain (G) a thermoplastic resin as an optional component. The (G) thermoplastic resin as this (G) component does not include those corresponding to the above-mentioned components (A) to (F).

[0137] Examples of the (G) thermoplastic resin include polyimide resin, phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, polyetheretherketone resin, polyester resin, etc. In one embodiment, the (G) thermoplastic resin preferably contains a thermoplastic resin selected from the group consisting of polyimide resin and phenoxy resin, and more preferably contains phenoxy resin. Further, the thermoplastic resin may be used alone or in combination of two or more.

[0138] Specific examples of the polyimide resin include "SLK-6100" manufactured by Shin-Etsu Chemical Co., Ltd., "Lica Coat SN20" and "Lica Coat PN20" manufactured by Shin Nippon Rika Co., Ltd., etc.

[0139] Examples of the phenoxy resin include phenoxy resins having one or more skeletons selected from the group consisting of a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a novolac skeleton, a biphenyl skeleton, a fluorene skeleton, a dicyclopentadiene skeleton, a norbornene skeleton, a naphthalene skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group.

[0140] Specific examples of the phenoxy resin include "1256" and "4250" manufactured by Mitsubishi Chemical Corporation (both are bisphenol A skeleton-containing phenoxy resins); "YX8100" manufactured by Mitsubishi Chemical Corporation (bisphenol S skeleton-containing phenoxy resin); "YX6954" manufactured by Mitsubishi Chemical Corporation (bisphenol acetophenone skeleton-containing phenoxy resin); "FX280" and "FX293" manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7482", and "YL7891BH30" manufactured by Mitsubishi Chemical Corporation; etc.

[0141] Examples of the polyvinyl acetal resin include a polyvinyl formal resin and a polyvinyl butyral resin, and the polyvinyl butyral resin is preferred. Specific examples of the polyvinyl acetal resin include "Denka Butyral 4000-2", "Denka Butyral 5000-A", "Denka Butyral 6000-C", "Denka Butyral 6000-EP" manufactured by Denka Co., Ltd.; Esrec BH series, BX series (e.g., BX-5Z), KS series (e.g., KS-1), BL series, BM series manufactured by Sekisui Chemical Co., Ltd.; etc.

[0142] Examples of polyolefin resins include ethylene-based copolymer resins such as low-density polyethylene, ultra-low density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-methyl acrylate copolymer; and polyolefin polymers such as polypropylene and ethylene-propylene block copolymer.

[0143] Examples of polybutadiene resins include resins containing a hydrogenated polybutadiene skeleton, hydroxy group-containing polybutadiene resins, phenolic hydroxyl group-containing polybutadiene resins, carboxy group-containing polybutadiene resins, acid anhydride group-containing polybutadiene resins, epoxy group-containing polybutadiene resins, isocyanate group-containing polybutadiene resins, urethane group-containing polybutadiene resins, polyphenylene ether-polybutadiene resins, and the like.

[0144] Specific examples of polyamideimide resins include "Vylon Max HR11NN" and "Vylon Max HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of polyamideimide resins also include modified polyamideimides such as "KS9100" and "KS9300" (polyamideimide containing a polysiloxane skeleton) manufactured by Hitachi Chemical Co., Ltd.

[0145] Specific examples of polyethersulfone resins include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd.

[0146] Specific examples of polysulfone resins include polysulfones "P1700" and "P3500" manufactured by Solvay Advanced Polymers, LLC.

[0147] Specific examples of polyphenylene ether resins include "NORYL SA90" manufactured by SABIC. Specific examples of polyetherimide resins include "ULTEM" manufactured by GE.

[0148] Examples of the polycarbonate resin include hydroxy group-containing carbonate resin, phenolic hydroxyl group-containing carbonate resin, carboxy group-containing carbonate resin, acid anhydride group-containing carbonate resin, isocyanate group-containing carbonate resin, urethane group-containing carbonate resin, and the like. Specific examples of the polycarbonate resin include "FPC0220" manufactured by Mitsubishi Gas Chemical Company, "T6002", "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemicals Corporation, "C-1090", "C-2090", "C-3090" (polycarbonate diol) manufactured by Kuraray Co., Ltd., and the like. Specific examples of the polyetheretherketone resin include "Sumipro EK" manufactured by Sumitomo Chemical Company, and the like.

[0149] Examples of the polyester resin include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polytrimethylene terephthalate resin, polytrimethylene naphthalate resin, polycyclohexanedimethylene terephthalate resin, and the like.

[0150] (G) From the viewpoint of significantly obtaining the effects of the present invention, the weight average molecular weight (Mw) of the thermoplastic resin is preferably 5,000 or more, more preferably 8,000 or more, still more preferably 10,000 or more, particularly preferably 20,000 or more, and preferably 100,000 or less, more preferably 70,000 or less, still more preferably 60,000 or less, particularly preferably 50,000 or less.

[0151] (G) From the viewpoint of significantly obtaining the desired effects of the present invention, when the non-volatile components in the resin composition are 100% by mass, the content of the thermoplastic resin is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, still more preferably 0.3% by mass or more, and preferably 5% by mass or less, more preferably 4% by mass or less, still more preferably 3% by mass or less.

[0152] <(H) Other Additives> In addition to the above-described components, the resin composition may further contain other additives as optional components. Examples of such additives include elastomers (excluding those corresponding to component (F) and component (G)), thickeners, defoamers, leveling agents, adhesion promoters, flame retardants, and the like. These may be used alone or in combination of two or more in any ratio.

[0153] The resin composition can be produced, for example, by mixing the above-described components in any order. Further, during the process of mixing each component, heating and / or cooling may be performed by appropriately adjusting the temperature. Also, during or after the mixing of each component, stirring may be performed using a stirring device such as a mixer to uniformly disperse each component. Furthermore, if necessary, a defoaming treatment may be performed on the resin composition.

[0154] <Physical properties and uses of the resin composition> Since the resin composition contains component (A), it is possible to obtain a cured product with a high glass transition temperature (Tg). Also, the resin composition can usually obtain a cured product with high peel strength and low dielectric tangent.

[0155] The cured product obtained by curing the resin composition at 190°C for 90 minutes exhibits the characteristic of having a high glass transition temperature (Tg). Therefore, it provides an insulating layer with a high glass transition temperature. The glass transition temperature of the cured product of the resin composition is preferably 145°C or higher, more preferably 150°C or higher, and even more preferably 155°C or higher. The upper limit is not particularly limited and can be, for example, 300°C or lower. The measurement of the glass transition temperature (Tg) can be performed by the method described in the examples below.

[0156] The cured product obtained by curing the resin composition at 130°C for 30 minutes and further at 170°C for 30 minutes exhibits the characteristic of having a high peel strength with plating. Therefore, when an insulating layer is formed with this cured product, an insulating layer with a high peel strength with the conductor layer can be obtained. The peel strength between the insulating layer and the conductor layer is preferably 0.3 kgf / cm or more, more preferably 0.35 kgf / cm or more, and still more preferably 0.4 kgf / cm or more. The upper limit is not particularly limited, but can be, for example, 10.0 kgf / cm or less. The peel strength can be measured by the method described in the examples below.

[0157] The cured product obtained by curing the resin composition at 190°C for 90 minutes exhibits the characteristic of having a low dielectric tangent. Therefore, when an insulating layer is formed with this cured product, an insulating layer with a low dielectric tangent can be obtained. The dielectric tangent of the cured product is preferably 0.006 or less, more preferably 0.005 or less, and still more preferably 0.004 or less. The lower limit is not particularly limited, but can be, for example, 0.0001 or more. The dielectric tangent can be measured by the method described in the examples below.

[0158] The resin composition of the present invention is suitable as a resin composition for insulation applications, and particularly suitable as a resin composition for forming an insulating layer. Therefore, for example, the resin composition is suitable as a resin composition for forming an insulating layer of a printed wiring board (a resin composition for forming an insulating layer of a printed wiring board). The resin composition is suitable as a resin composition for forming an interlayer insulating layer of a printed wiring board (a resin composition for forming an interlayer insulating layer of a printed wiring board). Further, the resin composition is suitable as a resin composition for forming an insulating layer for forming a conductor layer (including a rewiring layer) formed on the insulating layer (a resin composition for forming an insulating layer for forming a conductor layer). The resin composition can also be widely used in applications where resin compositions can be used, such as resin sheets, sheet-like laminated materials such as prepregs, solder resists, underfill materials, die bonding materials, semiconductor encapsulants, via filling resins, component embedding resins, multi-chip packages, package-on-package, wafer-level packages, panel-level packages, system-in-package, etc.

[0159] Also, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition according to the present embodiment is also suitable as a resin composition for forming a rewiring formation layer as an insulating layer for forming a rewiring layer (a resin composition for forming a rewiring formation layer), and a resin composition for encapsulating a semiconductor chip (a resin composition for encapsulating a semiconductor chip). When manufacturing a semiconductor chip package, a rewiring layer may be further formed on the encapsulation layer. (1) A step of laminating a temporary fixing film on a base material, (2) A step of temporarily fixing a semiconductor chip on the temporary fixing film, (3) A step of forming an encapsulation layer on the semiconductor chip, (4) A step of peeling the base material and the temporary fixing film from the semiconductor chip, (5) A step of 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, and (6) A step of forming a rewiring layer as a conductor layer on the rewiring formation layer

[0160] The above-described resin composition can also be used when the printed wiring board is a circuit board with built-in components.

[0161] [Resin sheet] The resin sheet of the present invention includes a support and a resin composition layer formed of the resin composition of the present invention provided on the support.

[0162] From the viewpoints of thinning the printed wiring board and providing a cured product excellent in insulation even if the cured product of the resin composition is a thin film, the thickness of the resin composition layer is preferably 100 μm or less, more preferably 75 μm or less, and still more preferably 50 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but can usually be 5 μm or more.

[0163] Examples of the support include a film made of a plastic material, a metal foil, and a release paper, and a film made of a plastic material and a metal foil are preferred.

[0164] When using a film made of a plastic material as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"), polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyethersulfide (PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

[0165] When using a metal foil as the support, examples of the metal foil include a copper foil and an aluminum foil, and a copper foil is preferred. As the copper foil, a foil made of single metal copper may be used, or a foil made of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.

[0166] The support may be subjected to matting treatment, corona treatment, or antistatic treatment on the surface that is joined to the resin composition layer.

[0167] Alternatively, as the support, a support with a release layer having a release layer on the surface that is joined to the resin composition layer may be used. Examples of the release agent used for the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. As the support with a release layer, a commercially available product may be used. For example, "SK-1", "AL-5", "AL-7" manufactured by Lintec Corporation, which are PET films having a release layer mainly composed of an alkyd resin-based release agent, "Lumirror T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Limited, "Unipile" manufactured by Unitika Ltd., etc. may be mentioned.

[0168] The thickness of the support is not particularly limited, but a range of 5 μm to 75 μm is preferable, and a range of 10 μm to 60 μm is more preferable. When using a support with a release layer, it is preferable that the total thickness of the support with a release layer is within the above range.

[0169] In one embodiment, the resin sheet may further include other layers as needed. Examples of such other layers include a protective film similar to the support provided on the surface of the resin composition layer that is not joined to the support (i.e., the surface opposite to the support). The thickness of the protective film is not particularly limited, but for example, it is 1 μm to 40 μm. By laminating the protective film, it is possible to suppress the adhesion of dust and scratches to the surface of the resin composition layer.

[0170] The resin sheet can be manufactured, for example, by preparing a resin varnish in which the resin composition is dissolved in an organic solvent, applying this resin varnish onto the support using a die coater or the like, and further drying to form a resin composition layer.

[0171] Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK), and cyclohexanone; acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide (DMAc), and N-methylpyrrolidone. The organic solvent may be used alone or in combination of two or more.

[0172] Drying may be carried out by known methods such as heating and hot air blowing. The drying conditions are not particularly limited, but the drying is carried out so that the content of the organic solvent in the resin composition layer is 10% 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 varnish, for example, when using a resin varnish containing 30% by mass to 60% by mass of the organic solvent, the resin composition layer can be formed by drying at 50°C to 150°C for 3 minutes to 10 minutes.

[0173] The resin sheet can be stored by winding it in a roll shape. When the resin sheet has a protective film, it can be used by peeling off the protective film.

[0174] [Printed Wiring Board] The printed wiring board according to an embodiment of the present invention includes an insulating layer formed of a cured product obtained by curing the above-described resin composition.

[0175] The printed wiring board can be manufactured, for example, by a method including the following steps (I) and (II) using the above-described resin sheet. (I) A step of laminating a resin sheet on an inner layer substrate so that the resin composition layer of the resin sheet is joined to the inner layer substrate (II) A step of curing the resin composition layer to form an insulating layer

[0176] The "inner layer substrate" used in Process (I) is a member that serves as the substrate of a printed wiring board. Examples thereof include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, and the like. Further, the substrate may have conductor layers on one or both sides thereof, and these conductor layers may be pattern-processed. An inner layer substrate having conductor layers formed on one or both sides of the substrate may be referred to as an "inner layer circuit board". Also, in the manufacture of a printed wiring board, intermediate products on which an insulating layer and / or a conductor layer are to be further formed are also included in the "inner layer substrate". When the printed wiring board is a component-embedded circuit board, an inner layer substrate incorporating components may be used.

[0177] The lamination of the inner layer substrate and the resin sheet can be performed, for example, by thermocompression bonding the resin sheet to the inner layer substrate from the support side. Examples of the member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter also referred to as the "thermocompression bonding member") include a heated metal plate (such as a SUS mirror plate) or a metal roll (such as a SUS roll). Note that it is preferable to press through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface unevenness of the inner layer substrate, rather than directly pressing the thermocompression bonding member against the resin sheet.

[0178] The lamination of the inner layer substrate and the resin sheet may be carried out by a vacuum lamination method. In the vacuum lamination method, the thermocompression bonding temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, the thermocompression bonding pressure is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably in the range of 0.29 MPa to 1.47 MPa, and the thermocompression bonding time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. The lamination can preferably be carried out under reduced pressure conditions of a pressure of 26.7 hPa or less.

[0179] The lamination can be carried out using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressurizing laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum applicator manufactured by Nichco Materials Co., Ltd., a batch-type vacuum pressurizing laminator, and the like.

[0180] After lamination, under atmospheric pressure, for example, by pressing a heat-bonding member from the support side, a smoothing process of the laminated resin sheet may be performed. The pressing conditions for the smoothing process can be the same as the heat-bonding conditions for the above lamination. The smoothing process can be performed by a commercially available laminator. Note that the lamination and the smoothing process may be continuously performed using the above-mentioned commercially available vacuum laminator.

[0181] The support may be removed between step (I) and step (II), or may be removed after step (II).

[0182] In step (II), the resin composition layer is cured to form an insulating layer made of a cured product of the resin composition. The curing conditions of the resin composition layer are not particularly limited, and the conditions employed when forming the insulating layer of a printed wiring board may be used. The resin composition layer may be cured by irradiation with active energy rays such as ultraviolet rays, but usually, it is thermally cured by heating.

[0183] For example, the thermal curing conditions of the resin composition layer vary depending on the type of the resin composition. In one embodiment, the curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, and even more preferably 170°C to 210°C. The curing time can be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and even more preferably 15 minutes to 100 minutes.

[0184] Before thermally curing the resin composition layer, 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.

[0185] The method for manufacturing a printed wiring board may further include the steps of (III) drilling holes in the insulating layer, (IV) roughening the insulating layer, and (V) forming a conductor layer. When removing the support 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). Further, if necessary, the formation of the insulating layer and the conductor layer in steps (I) to (V) may be repeated to form a multilayer wiring board.

[0186] Step (III) is a step of drilling holes in the insulating layer, by which holes such as via holes and through holes can be formed in the insulating layer. Step (III) may be carried out using, for example, a drill, a laser, a plasma, etc., according to the composition of the resin composition used for forming the insulating layer. The dimensions and shapes of the holes may be appropriately determined according to the design of the printed wiring board.

[0187] Step (IV) is a step of roughening the insulating layer. Usually, smear removal is also carried out in this step (IV). The procedures and conditions for the roughening treatment are not particularly limited. 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.

[0188] Examples of the swelling liquid used for the roughening treatment include an alkaline solution, a surfactant solution, etc., and an alkaline solution is preferred. As the alkaline solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferred. Examples of commercially available swelling liquids include "Swelling Dip Security Gun P" and "Swelling Dip Security Gun SBU" manufactured by Atotech Japan Co., Ltd. The swelling treatment with the swelling liquid is not particularly limited, but can be carried out, for example, by immersing the insulating layer in a swelling liquid at 30°C to 90°C for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40°C to 80°C for 5 minutes to 15 minutes.

[0189] Examples of the oxidizing agent used for the roughening treatment include an alkaline permanganate solution prepared by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably performed by immersing the insulating layer in the oxidizing agent solution heated to 60°C to 100°C for 10 minutes to 30 minutes. The concentration of the 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 Security Guard P" manufactured by Atotech Japan Co., Ltd.

[0190] The neutralizing solution used for the roughening treatment is preferably an acidic aqueous solution. Examples of commercially available products include "Reduction Solution Security Guard P" manufactured by Atotech Japan Co., Ltd. The treatment with the neutralizing solution can be performed by immersing the treated surface that has been roughened with the oxidizing agent in the neutralizing solution at 30°C to 80°C for 5 minutes to 30 minutes. From the viewpoint of workability and the like, a method of immersing the object that has been roughened with the oxidizing agent in the neutralizing solution at 40°C to 70°C for 5 minutes to 20 minutes is preferable.

[0191] In one embodiment, the arithmetic mean roughness Ra of the surface of the insulating layer after the roughening treatment can preferably be 500 nm or less, more preferably less than 200 nm, still more preferably 100 nm or less, and even more preferably less than 100 nm. The lower limit is not particularly limited and can be, for example, 1 nm or more, 2 nm or more, etc. Also, the root mean square roughness (Rq) of the surface of the insulating layer after the roughening treatment is preferably 500 nm or less, more preferably 400 nm or less, and still more preferably 300 nm or less. The lower limit is not particularly limited and can be, for example, 1 nm or more, 2 nm or more, etc. The arithmetic mean roughness (Ra) and the root mean square roughness (Rq) of the insulating layer surface can be measured using a non-contact surface roughness meter.

[0192] Step (V) is a step of forming a conductor layer, and the conductor layer is formed on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer contains one or more 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. Examples of the alloy layer include layers formed from alloys of two or more metals selected from the above group (for example, nickel-chromium alloys, copper-nickel alloys, and copper-titanium alloys). Among them, from the viewpoints of versatility in forming the conductor layer, cost, ease of patterning, etc., a single-metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy, copper-nickel alloy, or copper-titanium alloy is preferable, a single-metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy is more preferable, and a single-metal layer of copper is even more preferable.

[0193] The conductor layer may have a single-layer structure, or may have a multi-layer structure in which two or more single-metal layers or alloy layers made of different types of metals or alloys are laminated. When the conductor layer has a multi-layer structure, the layer in contact with the insulating layer is preferably a single-metal layer of chromium, zinc, or titanium, or an alloy layer of nickel-chromium alloy.

[0194] The thickness of the conductor layer depends on the design of the desired printed wiring board, but is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

[0195] The conductor layer is preferably formed by plating. For example, by plating on the surface of the insulating layer by methods such as semi-additive method or full-additive method, a conductor layer having a desired wiring pattern can be formed. From the viewpoint of manufacturing simplicity, it is preferably formed by the semi-additive method. Hereinafter, an example of forming the conductor layer by the semi-additive method is shown.

[0196] A plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer to expose a part of the plating seed layer corresponding to a desired wiring pattern. After forming a metal layer by electrolytic plating on the exposed plating seed layer, the mask pattern is removed. Thereafter, the unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern.

[0197] [Semiconductor device] The semiconductor device according to an embodiment of the present invention includes the printed wiring board described above. This semiconductor device can be manufactured using the printed wiring board described above.

[0198] Examples of the semiconductor device include various semiconductor devices used in electrical products (for example, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (for example, motorcycles, automobiles, trains, ships, airplanes, etc.).

Example

[0199] Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples. In the following description, "parts" and "%" representing amounts mean "parts by mass" and "mass%", respectively, unless otherwise specified. Also, the operations described below were performed in an environment of normal temperature and pressure unless otherwise specified.

[0200] <Example 1A> Synthesis of polyester resin (1) Into a 0.3-liter four-necked round flask equipped with a stirring device, thermometer, dropping funnel, and nitrogen gas inlet, 11.4 g of dicyclopentadiene-phenol polyadduct (J-DPP85 manufactured by JFE Chemical Co., Ltd., hydroxyl equivalent 165 g / eq.), 4.98 g of 1-naphthol, 10.0 g of 2,5-furandicarboxylic acid chloride, 0.026 g of tetra-n-butylammonium bromide, and 50 g of toluene were added. While blowing nitrogen gas, the mixture was stirred and heated to 30 °C to dissolve. Finally, 16.6 g of a 25% aqueous sodium hydroxide solution was added dropwise while paying attention to the exotherm so as to raise the temperature to 60 °C. The time required for dropping was 15 minutes. After further stirring at 60 °C for 1 hour, 25 g of distilled water was added, stirred, and the aqueous layer was discarded. The organic layer was washed three times in the same manner. The organic layer was dried over sodium sulfate, the drying agent was filtered off, and then a part of the solvent was distilled off from the obtained solution to obtain 24.7 g of the target polyester resin (1) (toluene solution containing 45% by mass of toluene, active group equivalent about 215 g / eq., biomass ratio 28.4% by mass, non-volatile component ratio 55%).

[0201] For the obtained polyester resin (1), measurements were carried out by gel permeation chromatography (GPC) method and infrared spectroscopic analysis (IR) method based on the following GPC measurement conditions and IR measurement conditions. The GPC chart of the polyester resin (1) is shown in Figure 1, and the IR chart is shown in Figure 2. In the mass spectrum (ESI) of the polyester resin (1), m / z = 407 (M-H) corresponding to n = 0 in the theoretical structure of the target substance - , m / z = 847 (M-H) corresponding to n = 1 - , 849 (M+H) + of each spectrum were observed. Also, the number average molecular weight of the polyester resin (1) by GPC was 1572. As a result, it was confirmed that the obtained polyester resin (1) has the following molecular structure (wherein n is 0 ≦ n ≦ 8, and a represents a number in the range of 0 to 4).

Chemical formula

[0202] (GPC measurement conditions) Measuring device: "HLC-8420GPC" manufactured by Tosoh Corporation Column: Guard column "HXL-L" manufactured by Tosoh Corporation + "TSK-GEL SuperHZ2000" manufactured by Tosoh Corporation + "TSK-GEL SuperHZ2000" manufactured by Tosoh Corporation + "TSK-GEL SuperHZ3000" manufactured by Tosoh Corporation + "TSK-GEL SuperHZ4000" manufactured by Tosoh Corporation Detector: RI (differential refractometer) Data processing: "GPC Workstation EcoSEC-WorkStation" manufactured by Tosoh Corporation Column temperature: 40 °C Developing solvent: Tetrahydrofuran Flow rate: 0.35 mL / min Standard: In accordance with the measurement manual of the "GPC Workstation EcoSEC-WorkStation", the following monodisperse polystyrene with a known molecular weight was used. TSKgel F-10, F-4, F-1, A-5000, A-1000, A-500 (manufactured by Tosoh Corporation) Sample: A 0.2 mass% tetrahydrofuran solution converted to resin solids, filtered through a microfilter (10 μL)

[0203] (IR measurement conditions) Measuring device: PIKE Technologiesshasei "GladiATR"

[0204] <Example 2A> Synthesis of polyester resin (2) Into a 0.3-liter four-neck round-bottom flask equipped with a stirring device, thermometer, dropping funnel, and nitrogen gas inlet, 10 g of dicyclopentadiene-phenol polyadduct (J-DPP85 manufactured by JFE Chemical Co., Ltd., hydroxyl equivalent 165 g / eq.), 4.4 g of 1-naphthol, 9.5 g of 2,5-thiophenedicarboxylic acid chloride, 0.024 g of tetra-n-butylammonium bromide, and 50 g of toluene were added. While blowing nitrogen gas, the mixture was stirred and heated to 30 °C to dissolve. Finally, 14.6 g of a 25% aqueous sodium hydroxide solution was added dropwise while paying attention to the exotherm so as to raise the temperature to 60 °C. The time required for the dropwise addition was 10 minutes. After further stirring at 60 °C for 1 hour, 25 g of distilled water was added and stirred, and then the aqueous layer was discarded. The organic layer was washed three times in the same manner. The organic layer was dried over sodium sulfate, and after filtering off the drying agent, a part of the solvent was distilled off from the obtained solution to obtain 27.6 g of the target polyester resin (2) (toluene solution containing 50% by mass of toluene, active group equivalent about 223 g / eq., biomass ratio 0% by mass, non-volatile component ratio 50%).

[0205] Regarding the obtained polyester resin (2), measurements were carried out by gel permeation chromatography (GPC) method and infrared spectroscopic analysis (IR) method under the same conditions as those for polyester resin (1). The GPC chart of polyester resin (2) is shown in Figure 3, and the IR chart is shown in Figure 4. Also, the number average molecular weight of polyester resin (2) by GPC was 2152. In the mass spectrum (ESI), m / z = 425 (M+H) corresponding to n = 0 and m / z = 882 (M+H) corresponding to n = 1 + were observed in each spectrum of the theoretical structure of the target substance. As a result, it was confirmed that the obtained polyester resin (2) has the following molecular structure (wherein n is 0 ≦ n ≦ 8, and a represents a number in the range of 0 to 4). + <Example 3A> Synthesis of Polyester Resin (3)

Chemical formula

[0207] In the esterification of Example 1A, 4.98 g of 1-naphthol was changed to 3.26 g of phenol. Except for the above matters, in the same manner as in Example 1A, a polyester resin (3) having the following molecular structure (toluene solution with a number average molecular weight of 1447, an active group equivalent of about 198 g / eq., a biomass ratio of 30.8% by mass, and a non-volatile component ratio of 55%) was obtained (wherein n is 0 ≦ n ≦ 8, and a represents a number in the range of 0 to 4).

Chemical formula

[0207] <Example 4A> Synthesis of polyester resin (4) In the esterification of Example 1A, 4.98 g of 1-naphthol was changed to 5.89 g of orthophenylphenol. Except for the above matters, in the same manner as in Example 1A, a polyester resin (4) having the following molecular structure (toluene solution with a number average molecular weight of 1889, an active group equivalent of about 224 g / eq., a biomass ratio of 27.3% by mass, and a non-volatile component ratio of 55%) was obtained (wherein n is 0 ≦ n ≦ 8, and a represents a number in the range of 0 to 4).

Chemical formula

[0208] <Example 5A> Synthesis of polyester resin (5) In the esterification of Example 1A, 11.4 g of a dicyclopentadiene-phenol adduct (「J-DPP85」manufactured by JFE Chemical Co., Ltd., hydroxyl group equivalent 165 g / eq.) was changed to 58.8 g of SA90 (manufactured by SABIC Innovative Plastics). Except for the above matters, in the same manner as in Example 1A, a polyester resin (5) having the following molecular structure (toluene solution containing 70% by mass of toluene, with a number average molecular weight of 4652, an active group equivalent of about 675 g / eq., a biomass ratio of 9.0% by mass, and a non-volatile component ratio of 30%) was obtained (wherein n is 0 ≦ n ≦ 8, and b, c represent numbers in the range of 0 to 4).

Chemical formula

[0209] <Example 6A> Synthesis of Polyester Resin (6) In the esterification of Example 1A, 11.4 g of dicyclopentadiene-phenol adduct (“J-DPP85” manufactured by JFE Chemical Co., hydroxyl equivalent 165 g / eq.) was changed to 9.28 g of 3-(4-hydroxyphenyl)-1,1,3-trimethyl-2,3-dihydro-1H-inden-5-ol. Except for the above matters, in the same manner as in Example 1A, a polyester resin (6) having the following molecular structure (number average molecular weight 1297, active group equivalent about 198 g / eq., biomass ratio 30.9% by mass, toluene solution with non-volatile component ratio 55%) was obtained (wherein n is 0 ≦ n ≦ 8).

Chemical formula

[0210] <Example 7A> Synthesis of Polyester Resin (7) In the esterification of Example 1A, 11.4 g of dicyclopentadiene-phenol adduct (“J-DPP85” manufactured by JFE Chemical Co., hydroxyl equivalent 165 g / eq.) was changed to 12.1 g of 4,4'-(9-fluorenylidene)diphenol. Except for the above matters, in the same manner as in Example 1A, a polyester resin (7) having the following molecular structure (1585, active group equivalent about 225 g / eq., biomass ratio 27.1% by mass, toluene solution with non-volatile component ratio 55%) was obtained (wherein n is 0 ≦ n ≦ 8).

Chemical formula

[0211] <Example 8A> Synthesis of Polyester Resin (8) In the esterification of Example 1A, 11.4 g of the dicyclopentadiene-phenol adduct (“J-DPP85” manufactured by JFE Chemical Corporation, hydroxyl equivalent weight 165 g / eq.) was changed to 7.00 g of 4,4'-dihydroxydiphenyl ether. Except for the above matters, in the same manner as in Example 1A, a polyester resin (8) having the following molecular structure (number average molecular weight 1278, active group equivalent weight approximately 175 g / eq., biomass ratio 34.8% by mass, toluene solution with non-volatile component ratio 55%) was obtained (wherein n is 0 ≦ n ≦ 8).

Chemical formula

[0212] <Example 9A> Synthesis of polyester resin (9) In the esterification of Example 1A, 11.4 g of the dicyclopentadiene-phenol adduct (“J-DPP85” manufactured by JFE Chemical Corporation, hydroxyl equivalent weight 165 g / eq.) was changed to 7.41 g of 4,4'-dihydroxybenzophenone. Except for the above matters, in the same manner as in Example 1A, a polyester resin (9) having the following molecular structure (number average molecular weight 1198, active group equivalent weight approximately 179 g / eq., biomass ratio 34.0% by mass, toluene solution with non-volatile component ratio 55%) was obtained (wherein n is 0 ≦ n ≦ 8).

Chemical formula

[0213] <Example 10A> Synthesis of polyester resin (10) In the esterification of Example 1A, 11.4 g of the dicyclopentadiene-phenol adduct (“J-DPP85” manufactured by JFE Chemical Corporation, hydroxyl equivalent weight 165 g / eq.) was changed to 7.90 g of bisphenol A. Except for the above matters, in the same manner as in Example 1A, a polyester resin (10) having the following molecular structure (number average molecular weight 1254, active group equivalent weight approximately 184 g / eq., biomass ratio 33.1% by mass, toluene solution with non-volatile component ratio 55%) was obtained (wherein n is 0 ≦ n ≦ 8).

Chemical formula

[0214] <Example 11A> Synthesis of polyester resin (11) In the esterification of Example 1A, 11.4 g of dicyclopentadiene-phenol adduct (“J-DPP85” manufactured by JFE Chemical Co., hydroxyl equivalent 165 g / eq.) was changed to 6.93 g of bisphenol F. Except for the above matters, in the same manner as in Example 1A, a polyester resin (11) having the following molecular structure (toluene solution with number average molecular weight 1168, active group equivalent about 175 g / eq., biomass ratio 34.9 mass%, non-volatile component ratio 55%) was obtained (wherein n is 0 ≦ n ≦ 8).

Chemical formula

[0215] <Example 12A> Synthesis of polyester resin (12) In the esterification of Example 1A, 11.4 g of dicyclopentadiene-phenol adduct (“J-DPP85” manufactured by JFE Chemical Co., hydroxyl equivalent 165 g / eq.) was changed to 10.7 g of 2,2'-diallylbisphenol A. Except for the above matters, in the same manner as in Example 1A, a polyester resin (12) having the following molecular structure (toluene solution with number average molecular weight 1468, active group equivalent about 211 g / eq., biomass ratio 28.9 mass%, non-volatile component ratio 55%) was obtained (wherein n is 0 ≦ n ≦ 8).

Chemical formula

[0216] <Example 13A> Synthesis of polyester resin (13) In the esterification of Example 1A, 11.4 g of a dicyclopentadiene-phenol adduct (“J-DPP85” manufactured by JFE Chemical Corporation, hydroxyl equivalent weight 165 g / eq.) was changed to 8.66 g of bisphenol S. Except for the above matters, in the same manner as in Example 1A, a polyester resin (13) having the following molecular structure (number average molecular weight 1367, active group equivalent weight approximately 192 g / eq., biomass ratio 31.9% by mass, toluene solution with non-volatile component ratio 55%) was obtained (wherein n is 0 ≦ n ≦ 8).

Chemical formula

[0217] <Example 14A> Synthesis of polyester resin (14) In the esterification of Example 1A, 11.4 g of a dicyclopentadiene-phenol adduct (“J-DPP85” manufactured by JFE Chemical Corporation, hydroxyl equivalent weight 165 g / eq.) was changed to 6.44 g of 4,4'-dihydroxybiphenyl. Except for the above matters, in the same manner as in Example 1A, a polyester resin (14) having the following molecular structure (number average molecular weight 1231, active group equivalent weight approximately 170 g / eq., biomass ratio 35.9% by mass, toluene solution with non-volatile component ratio 55%) was obtained (wherein n is 0 ≦ n ≦ 8).

Chemical formula

[0218] <Example 15A> Synthesis of polyester resin (15) In the esterification of Example 1A, 11.4 g of a dicyclopentadiene-phenol adduct (“J-DPP85” manufactured by JFE Chemical Corporation, hydroxyl equivalent weight 165 g / eq.) was changed to 5.54 g of 2,7-naphthalenediol. Except for the above matters, in the same manner as in Example 1A, a polyester resin (15) having the following molecular structure (number average molecular weight 1128, active group equivalent weight approximately 161 g / eq., biomass ratio 37.8% by mass, toluene solution with non-volatile component ratio 55%) was obtained (wherein n is 0 ≦ n ≦ 8).

Chemical formula

[0219] <Example 16A> Synthesis of Polyester Resin (16) Into a 0.3-liter four-necked round flask equipped with a stirrer, thermometer, dropping funnel, and nitrogen gas inlet, 20.0 g of bisphenol A (hydroxyl equivalent weight 114 g / eq.), 8.1 g of phenol, 25.0 g of 2,5-furandicarboxylic acid chloride, 0.053 g of tetra-n-butylammonium bromide, and 70 g of toluene were added. While blowing nitrogen gas, the mixture was stirred and heated to 30 °C to dissolve. Finally, 48 g of a 25% aqueous sodium hydroxide solution was added dropwise while paying attention to the exotherm so as to raise the temperature to 60 °C. The time required for dropping was 15 minutes. After further stirring at 60 °C for 1 hour, 25 g of distilled water was added, stirred, and the aqueous layer was discarded. The organic layer was washed 3 times in the same manner. The organic layer was dried over sodium sulfate, the drying agent was filtered off, and then a part of the solvent was distilled off from the obtained solution to obtain a polyester resin (16) (number average molecular weight 917, active group equivalent weight approximately 153 g / eq., biomass ratio > 99 mass%, toluene solution with non-volatile component ratio 45%) with a solid content concentration of 45 mass%.

[0220] Regarding the obtained polyester resin (16), measurements were carried out by gel permeation chromatography (GPC) method and infrared spectroscopy (IR) method under the same conditions as those for polyester resin (1). The number average molecular weight of the polyester resin by GPC was 917. The GPC chart of the polyester resin is shown in Figure 5, and the IR chart is shown in Figure 6. Also, in the mass spectrum (ESI), m / z = 309 (M+H) corresponding to n = 0 and m / z = 658 (M+2H) corresponding to n = 1 + in the theoretical structure of the target substance were observed. As a result, it was confirmed that the obtained polyester resin has the following molecular structure. In the formula, n represents a number in the range of 0 ≦ n ≦ 8. 2+

[0221] ​​<Example 17A> Synthesis of Polyester Resin (17) In Example 1A, 1) Change 4.98 g of 1-naphthol to 8.0 g of camphene-modified phenol ("YS Resin CP" manufactured by Yasuhara Chemical Co., Ltd., hydroxyl equivalent weight 220 g / eq.), 2) Change 11.4 g of dicyclopentadiene-phenol polyadduct ("J-DPP85" manufactured by JFE Chemical Corporation, hydroxyl equivalent weight 165 g / eq.) to 7.9 g of bisphenol A (hydroxyl equivalent weight 114 g / eq.). Except for the above matters, in the same manner as in Example 1A, a polyester resin (17) having the following molecular structure (toluene solution with number average molecular weight 1348, active group equivalent weight of about 225 g / eq., biomass ratio 88% by mass, non-volatile component ratio 55%) was obtained.

[0222] Regarding the obtained polyester resin (17), measurements were carried out by gel permeation chromatography (GPC) method and infrared spectroscopic analysis (IR) method under the same conditions as those for polyester resin (1). The number average molecular weight of the polyester resin by GPC was 1348. The GPC chart of the polyester resin is shown in Figure 7, and the IR chart is shown in Figure 8. Also, in the mass spectrum (ESI), m / z = 581 (M + H) corresponding to n = 0 in the theoretical structure of the target substance + , m / z = 942 (M + Na) corresponding to n = 1 + were observed for each spectrum. As a result, it was confirmed that the obtained polyester resin has the following molecular structure. In the formula, n represents a number in the range of 0 ≦ n ≦ 8. [Chemical formula]

[0223] <Example 18A> Synthesis of Polyester Resin (18) In Example 1A, 1) Change 4.98 g of 1-naphthol to 3.3 g of phenol, 2) 11.4 g of dicyclopentadiene-phenol polyadduct (J-DPP85 manufactured by JFE Chemical Co., Ltd., hydroxyl equivalent weight 165 g / eq.) was changed to 14 g of benzyl-modified bisphenol A (in the following formula, d and e each represent an integer from 1 to 4, satisfying 1 ≦ d + e ≦ 4). Except for the above matters, in the same manner as in Example 1A, a polyester resin (18) having the following molecular structure (number average molecular weight 433, active group equivalent weight approximately 217 g / eq., biomass ratio 71% by mass (n = 1 and d + e = 3), toluene solution with non-volatile component ratio 46%) was obtained.

[0224] For the obtained polyester resin (18), measurements were carried out by gel permeation chromatography (GPC) method and infrared spectroscopy (IR) method under the same conditions as for the polyester resin (1). The number average molecular weight of the polyester resin by GPC was 433. The GPC chart of the polyester resin is shown in Figure 9, and the IR chart is shown in Figure 10. Also, in the mass spectrum (ESI), m / z = 309 (M + H) corresponding to n = 0 in the theoretical structure of the target substance + , m / z = 968 (M + MeCN + H) corresponding to n = 1 and d + e = 3 + of each spectrum was observed. As a result, it was confirmed that the obtained polyester resin has the following molecular structure. In the formula, n is 0 ≦ n ≦ 8, d and e each represent an integer from 0 to 4, and satisfy the range of 1 ≦ d + e ≦ 4.

Chemical formula

[0225] <Example 1B> Preparation of resin composition and production of resin sheet 15 parts of bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, "828EL", epoxy equivalent of about 180 g / eq., biomass ratio 0 mass%), 20 parts of biphenyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., "NC3000L", epoxy equivalent of about 269 g / eq., biomass ratio 0 mass%), and 20 parts of naphthalene type epoxy resin (manufactured by Nippon Steel Chemical & Material Co., Ltd., "ESN475V", epoxy equivalent of about 332 g / eq., biomass ratio 0 mass%) were stirred to prepare an epoxy resin dissolved composition. To this epoxy resin dissolved composition, 5 parts of a phenolic curing agent containing a triazine skeleton (manufactured by DIC Corporation, "LA-3018-50P", active group equivalent of about 151 g / eq., biomass ratio 0 mass%, 2-methoxypropanol solution with a non-volatile component rate of 50%), 40 parts of the polyester resin (1) obtained in Example 1A (toluene solution with an active group equivalent of about 215 g / eq., biomass ratio 28.4 mass%, non-volatile component rate 55%), 4 parts of an amine-based curing accelerator (4-dimethylaminopyridine (DMAP), biomass ratio 0 mass%, MEK solution with a solid content of 5 mass%), 200 parts of spherical silica surface-treated with a silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-573") (manufactured by Admatechs Co., Ltd., "SO-C2", average particle size 0.5 μm, biomass ratio 0 mass%), and 8 parts of a phenoxy resin (manufactured by Mitsubishi Chemical Corporation, "YX7553BH30", biomass ratio 0 mass%, 1:1 solution of MEK and cyclohexanone with a non-volatile content of 30 mass%) were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish.

[0226] Next, the resin varnish was uniformly applied onto the release surface of a polyethylene terephthalate film with a release treatment (manufactured by Lintec Corporation, "AL5", thickness 38 μm) which is a support so that the thickness of the resin composition layer would be 40 μm, and dried at 80 to 120 °C (average 100 °C) for 5 minutes to produce a resin sheet.

[0227] <Example 2B> Preparation of Resin Composition and Production of Resin Sheet In Example 1B, 1) The amount of the polyester resin (1) synthesized in Example 1A (toluene solution with an active group equivalent of about 215 g / eq., biomass ratio of 28.4% by mass, and non-volatile component ratio of 55%) was changed from 40 parts to 20 parts. 2) 15 parts of an active ester compound ("HPC-8000-65T" manufactured by DIC, toluene solution with an active group equivalent of about 223 g / eq., biomass ratio of 0% by mass, and non-volatile component ratio of 65%) was further used. 3) The amount of spherical silica ("SO-C2" manufactured by Admatechs, average particle size 0.5 μm, biomass ratio of 0% by mass) surface-treated with a silane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.) was changed from 200 parts to 55 parts. 4) The amount of the phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, 1:1 solution of MEK and cyclohexanone with a biomass ratio of 0% by mass and non-volatile content of 30% by mass) was changed from 8 parts to 12 parts. A resin varnish and a resin sheet were prepared in the same manner as in Example 1B except for the above matters.

[0228] <Example 3B> In Example 1B, 1) 20 parts of a biphenyl-type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 269 g / eq., biomass ratio of 0% by mass) was changed to 20 parts of a bixylenol-type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 194 g / eq., biomass ratio of 0% by mass). 2) 40 parts of the polyester resin (1) obtained in Example 1A (toluene solution with an active group equivalent of about 223 g / eq., biomass ratio of 28.4% by mass, and non-volatile component ratio of 55%) was changed to 44 parts of the polyester resin (2) obtained in Example 2 (toluene solution with an active group equivalent of about 223 g / eq., biomass ratio of 0% by mass, and non-volatile component ratio of 50%). A resin varnish and a resin sheet were prepared in the same manner as in Example 1B except for the above matters.

[0229] <Example 4B> In Example 1B, 1) Replace 20 parts of biphenyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., "NC3000L", epoxy equivalent of about 269 g / eq., biomass ratio 0% by mass) with 20 parts of naphthylene ether type epoxy resin (manufactured by DIC Corporation, "HP-6000", epoxy equivalent of about 250 g / eq., biomass ratio 0% by mass). 2) Replace 40 parts of the polyester resin (1) obtained in Example 1A (toluene solution with an active group equivalent of about 223 g / eq., biomass ratio 28.4% by mass, non-volatile component ratio 55%) with 40 parts of the polyester resin (3) obtained in Example 3A (toluene solution with an active group equivalent of about 198 g / eq., biomass ratio 30.8% by mass, non-volatile component ratio 55%). Resin varnish and resin sheet were prepared in the same manner as in Example 1B except for the above matters.

[0230] <Example 5B> In Example 1B, 1) Replace 20 parts of naphthalene type epoxy resin (manufactured by Nippon Steel Chemical & Material Co., Ltd., "ESN475V", epoxy equivalent of about 332 g / eq., biomass ratio 0% by mass) with 15 parts of dicyclopentadiene type epoxy resin (manufactured by DIC Corporation, "HP-7200HH", epoxy equivalent of about 280 g / eq., biomass ratio 0% by mass). 2) Further use 6 parts of epoxidized polybutadiene resin (manufactured by Daicel Corporation, "PB3600M", non-volatile content 80% by mass, epoxy equivalent of about 193 g / eq.). 3) Replace 40 parts of the polyester resin (1) obtained in Example 1A (toluene solution with an active group equivalent of about 223 g / eq., biomass ratio 28.4% by mass, non-volatile component ratio 55%) with 40 parts of the polyester resin (4) obtained in Example 4A (toluene solution with an active group equivalent of about 224 g / eq., biomass ratio 27.3% by mass, non-volatile component ratio 55%). Resin varnish and resin sheet were prepared in the same manner as in Example 1B except for the above matters.

[0231] <Example 6B> In Example 1B, 1) Replace 5 parts of the phenolic curing agent containing a triazine skeleton (DIC's "LA-3018-50P", active group equivalent of about 151 g / eq., biomass ratio 0% by mass, 2-methoxypropanol solution with a non-volatile component ratio of 50%) with 3 parts of a naphthol type curing agent (Nippon Steel Chemical & Material's "SN-485", hydroxyl group equivalent of about 205 g / eq., biomass ratio 0% by mass). 2) Replace 40 parts of the polyester resin (1) obtained in Example 1A (toluene solution with an active group equivalent of about 223 g / eq., biomass ratio 28.4% by mass, non-volatile component ratio 55%) with 72 parts of the polyester resin (5) obtained in Example 5 (toluene solution with an active group equivalent of about 675 g / eq., biomass ratio 9.0% by mass, non-volatile component ratio 30%). Resin varnish and resin sheet were prepared in the same manner as in Example 1B except for the above matters.

[0232] <Example 7B> In Example 1, 1) Use 5 parts of a prepolymer of bisphenol A dicyanate (Lonza Japan's "BA230S75", cyanate equivalent of about 232 g / eq., biomass ratio 0% by mass, MEK solution with 75% by mass of non-volatile matter). 2) Replace 40 parts of the polyester resin (1) obtained in Example 1A (toluene solution with an active group equivalent of about 223 g / eq., biomass ratio 28.4% by mass, non-volatile component ratio 55%) with 40 parts of the polyester resin (6) obtained in Example 6 (toluene solution with an active group equivalent of about 198 g / eq., biomass ratio 30.9% by mass, non-volatile component ratio 55%). 3) Further use 2 parts of a 1% by mass MEK solution of cobalt(III) acetylacetonate ((Co(III), manufactured by Tokyo Chemical Industry, biomass ratio 0% by mass)). Resin varnish and resin sheet were prepared in the same manner as in Example 1B except for the above matters.

[0233] <Example 8B> In Example 1B, 1) Replace 40 parts of the polyester resin (1) obtained in Example 1A (toluene solution with an active group equivalent of about 223 g / eq., biomass ratio of 28.4% by mass, and non-volatile component ratio of 55%) with 40 parts of the polyester resin (7) obtained in Example 7 (toluene solution with an active group equivalent of about 225 g / eq., biomass ratio of 27.1% by mass, and non-volatile component ratio of 55%). 2) Replace 4 parts of the amine-based curing accelerator (4-dimethylaminopyridine (DMAP), toluene solution with a biomass ratio of 0% by mass and a solid content of 5% by mass) with 3 parts of the imidazole-based curing accelerator (manufactured by Shikoku Kasei Kogyo Co., Ltd., "1B2PZ", 1-benzyl-2-phenylimidazole, toluene solution with a solid content of 10% by mass). A resin varnish and a resin sheet were prepared in the same manner as in Example 1B except for the above matters.

[0234] <Example 9B> In Example 1B, 1) Replace 40 parts of the polyester resin (1) obtained in Example 1A (toluene solution with an active group equivalent of about 223 g / eq., biomass ratio of 28.4% by mass, and non-volatile component ratio of 55%) with 40 parts of the polyester resin (8) obtained in Example 8 (toluene solution with an active group equivalent of about 175 g / eq., biomass ratio of 34.8% by mass, and non-volatile component ratio of 55%). 2) Further use 3 parts of rubber particles (manufactured by Aika Kogyo Co., Ltd., "Stafiloid AC3816N", biomass ratio of 0% by mass). A resin varnish and a resin sheet were prepared in the same manner as in Example 1B except for the above matters.

[0235] <Example 10B> In Example 1B, 1) Replace 40 parts of the polyester resin (1) obtained in Example 1A (toluene solution with an active group equivalent of about 223 g / eq., biomass ratio of 28.4% by mass, and non-volatile component ratio of 55%) with 40 parts of the polyester resin (9) obtained in Example 9A (toluene solution with an active group equivalent of about 179 g / eq., biomass ratio of 34.0% by mass, and non-volatile component ratio of 55%). 2) 7 parts of biphenyl aralkyl novolak type maleimide (MEK / toluene mixed solution of "MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., non-volatile component ratio 70%) was further used. Resin varnish and resin sheet were produced in the same manner as in Example 1B except for the above matters.

[0236] <Example 11B> In Example 1B, 1) 40 parts of the polyester resin (1) obtained in Example 1A (toluene solution with an active group equivalent of about 223 g / eq., biomass ratio of 28.4% by mass, non-volatile component ratio of 55%) was changed to 40 parts of the polyester resin (10) obtained in Example 10A (toluene solution with an active group equivalent of about 184 g / eq., biomass ratio of 33.1% by mass, non-volatile component ratio of 55%). 2) 5 parts of a bismaleimide-terminated polyimide compound ("BMI-1500" manufactured by DMI) was further used. Resin varnish and resin sheet were produced in the same manner as in Example 1B except for the above matters.

[0237] <Example 12B> In Example 1B, 1) 40 parts of the polyester resin (1) obtained in Example 1 (toluene solution with an active group equivalent of about 223 g / eq., biomass ratio of 28.4% by mass, non-volatile component ratio of 55%) was changed to 40 parts of the polyester resin (11) obtained in Example 11 (toluene solution with an active group equivalent of about 175 g / eq., biomass ratio of 34.9% by mass, non-volatile component ratio of 55%). 2) 8 parts of vinylbenzyl-modified polyphenylene ether ("OPE-2St 2200" manufactured by Mitsubishi Gas Chemical Company, toluene solution with a non-volatile component ratio of 65%) was further used. Resin varnish and resin sheet were produced in the same manner as in Example 1B except for the above matters.

[0238] <Example 13B> In Example 1B, 1) Replace 40 parts of the polyester resin (1) obtained in Example 1A (toluene solution with an active group equivalent of about 223 g / eq., biomass ratio of 28.4% by mass, and non-volatile component ratio of 55%) with 40 parts of the polyester resin (12) obtained in Example 12A (toluene solution with an active group equivalent of about 211 g / eq., biomass ratio of 28.9% by mass, and non-volatile component ratio of 55%). 2) Replace 200 parts of spherical silica (manufactured by Admatechs Co., Ltd. "SO-C2", average particle size 0.5 μm, biomass ratio 0% by mass) surface-treated with a silane coupling agent (Shin-Etsu Chemical Co., Ltd. "KBM-573") with 55 parts of spherical silica (manufactured by Denka Co., Ltd. "UFP-30", average particle size 0.3 μm, biomass ratio 0% by mass) surface-treated with a silane coupling agent (Shin-Etsu Chemical Co., Ltd. "KBM-573"). 3) Change the amount of the phenoxy resin (manufactured by Mitsubishi Chemical Corporation "YX7553BH30", biomass ratio 0% by mass, 1:1 solution of MEK and cyclohexanone with a non-volatile content of 30% by mass) from 8 parts to 12 parts. A resin varnish and a resin sheet were prepared in the same manner as in Example 1B except for the above matters.

[0239] <Example 14B> In Example 1B, 1) Replace 40 parts of the polyester resin (1) obtained in Example 1A (toluene solution with an active group equivalent of about 223 g / eq., biomass ratio of 28.4% by mass, and non-volatile component ratio of 55%) with 40 parts of the polyester resin (13) obtained in Example 13A (toluene solution with an active group equivalent of about 192 g / eq., biomass ratio of 31.9% by mass, and non-volatile component ratio of 55%). 2) Change the amount of the amine-based curing accelerator (4-dimethylaminopyridine (DMAP), biomass ratio 0% by mass, MEK solution with a solid content of 5% by mass) from 4 parts to 2 parts. 3) Further use 1.5 parts of an imidazole-based curing accelerator (manufactured by Shikoku Kasei Kogyo Co., Ltd. "1B2PZ", 1-benzyl-2-phenylimidazole MEK solution with a solid content of 10% by mass). A resin varnish and a resin sheet were prepared in the same manner as in Example 1B except for the above matters.

[0240] <Example 15B> In Example 1B, 1) 40 parts of the polyester resin (1) obtained in Example 1A (toluene solution with an active group equivalent of about 223 g / eq., biomass ratio of 28.4% by mass, and non-volatile component ratio of 55%) was changed to 40 parts of the polyester resin (14) obtained in Example 14A (toluene solution with an active group equivalent of about 170 g / eq., biomass ratio of 35.9% by mass, and non-volatile component ratio of 55%), 2) 8 parts of vinylbenzyl-modified polyphenylene ether (「OPE-2St 2200」manufactured by Mitsubishi Gas Chemical Company, toluene solution with a non-volatile component ratio of 65%) was further used, 3) 8 parts of phenoxy resin (「YX7553BH30」manufactured by Mitsubishi Chemical Corporation, 1:1 solution of MEK and cyclohexanone with a biomass ratio of 0% by mass and non-volatile content of 30% by mass) was not used. A resin varnish and a resin sheet were prepared in the same manner as in Example 1B except for the above matters.

[0241] <Example 16B> In Example 1B, 1) The amount of the naphthalene-type epoxy resin (「ESN475V」manufactured by Nippon Steel Chemical & Material Co., Ltd., epoxy equivalent of about 332 g / eq., biomass ratio of 0% by mass) was changed from 20 parts to 15 parts, 2) 6 parts of an epoxidized polybutadiene resin (「PB3600M」manufactured by Daicel Corporation, non-volatile content of 80% by mass, epoxy equivalent of about 193 g / eq.) was further used, 3) 40 parts of the polyester resin (1) obtained in Example 1A (toluene solution with an active group equivalent of about 223 g / eq., biomass ratio of 28.4% by mass, and non-volatile component ratio of 55%) was changed to 40 parts of the polyester resin (15) obtained in Example 15A (toluene solution with an active group equivalent of about 161 g / eq., biomass ratio of 37.8% by mass, and non-volatile component ratio of 55%), 4) The amount of spherical silica (「SO-C2」manufactured by Admatechs Co., Ltd., average particle size of 0.5 μm, biomass ratio of 0% by mass) surface-treated with a silane coupling agent (「KBM-573」manufactured by Shin-Etsu Chemical Co., Ltd.) was changed from 200 parts to 245 parts, 5) The amount of the phenoxy resin (「YX7553BH30」manufactured by Mitsubishi Chemical Corporation, a 1:1 solution of MEK and cyclohexanone with a biomass ratio of 0% by mass and a non-volatile content of 30% by mass) was changed from 8 parts to 5 parts. Resin varnish and resin sheets were produced in the same manner as in Example 1B except for the above matters.

[0242] <Example 17B> In Example 1B, 1) The amount of the polyester resin (1) synthesized in Example 1A (a toluene solution with an active group equivalent of about 215 g / eq., a biomass ratio of 28.4% by mass, and a non-volatile component ratio of 55%) was changed from 40 parts to 20 parts. 2) 24 parts of the polyester resin (16) synthesized in Example 16A (a toluene solution with an active group equivalent of about 153 g / eq., a biomass ratio > 99% by mass, and a non-volatile component ratio of 45%) was further used. Resin varnish and resin sheets were produced in the same manner as in Example 1B except for the above matters.

[0243] <Example 18B> In Example 1B, 1) The amount of the polyester resin (1) synthesized in Example 1A (a toluene solution with an active group equivalent of about 215 g / eq., a biomass ratio of 28.4% by mass, and a non-volatile component ratio of 55%) was changed from 40 parts to 20 parts. 2) 20 parts of the polyester resin (17) synthesized in Example 17A (a toluene solution with an active group equivalent of about 225 g / eq., a biomass ratio of 88% by mass, and a non-volatile component ratio of 55%) was further used. Resin varnish and resin sheets were produced in the same manner as in Example 1B except for the above matters.

[0244] <Example 19B> In Example 1B, 1) The amount of the polyester resin (1) synthesized in Example 1A (a toluene solution with an active group equivalent of about 215 g / eq., a biomass ratio of 28.4% by mass, and a non-volatile component ratio of 55%) was changed from 40 parts to 20 parts. 2) 24 parts of the polyester resin (18) synthesized in Example 18A (toluene solution with an active group equivalent of about 217 g / eq., a biomass ratio of 71% by mass (n = 1 and d + e = 3), and a non-volatile content rate of 46%) was further used. Except for the above matters, a resin varnish and a resin sheet were produced in the same manner as in Example 1B.

[0245] <Comparative Example 1> In Example 1B, 40 parts of the polyester resin (1) obtained in Example 1 (toluene solution with an active group equivalent of about 215 g / eq., a biomass ratio of 28.4% by mass, and a non-volatile content rate of 55%) was changed to 35 parts of an active ester compound ("HPC-8000-65T" manufactured by DIC, toluene solution with an active group equivalent of about 223 g / eq., a biomass ratio of 0% by mass, and a non-volatile content rate of 65%). Except for the above matters, a resin varnish and a resin sheet were produced in the same manner as in Example 1B.

[0246] <Measurement of Plating Peel Strength> (1) Preparation of a Substrate-Treated Inner Layer Substrate A glass cloth base epoxy resin double-sided copper-clad laminate having a copper foil on the surface (copper foil thickness: 18 μm, substrate thickness: 0.8 mm, "R1515A" manufactured by Panasonic) was prepared. The copper foil on the surface of this inner layer substrate was etched with a micro-etching agent ("CZ8101" manufactured by Meck) at a copper etching amount of 1 μm to perform a roughening treatment. Then, drying was performed at 190°C for 30 minutes to prepare a substrate-treated inner layer substrate.

[0247] (2) Lamination and Curing of the Resin Sheet The resin sheets obtained in the examples and comparative examples were laminated on both sides of the inner layer substrate with the ground treatment so that the resin composition layer was joined to the inner layer substrate with the ground treatment using a batch type vacuum pressure laminator (two-stage build-up laminator "CVP700" manufactured by Nikko Materials Co., Ltd.). This lamination was carried out by reducing the pressure for 30 seconds to make the atmospheric pressure 13 hPa or less, and then performing pressure bonding at a temperature of 100 °C and a pressure of 0.74 MPa for 30 seconds. Next, the laminated resin sheet was hot pressed at 100 °C and a pressure of 0.5 MPa for 60 seconds under atmospheric pressure to smooth it. Further, this was put into an oven at 130 °C and heated for 30 minutes, and then transferred to an oven at 170 °C and heated for 30 minutes to obtain a substrate A with a cured resin layer.

[0248] (3) Formation of conductor layer by plating After peeling the support from the substrate A with a cured resin layer, it was immersed in Swelling Dip Security Gun P manufactured by Atotech Japan, which is a swelling liquid, at 60 °C for 10 minutes. Next, it was immersed in Concentrate Compact P manufactured by Atotech Japan, which is a roughening liquid (aqueous solution of KMnO4: 60 g / L, NaOH: 40 g / L), at 80 °C for 20 minutes. Finally, it was immersed in Reduction Solution Security Gun P manufactured by Atotech Japan, which is a neutralizing liquid, at 40 °C for 5 minutes. Subsequently, it was immersed in a solution for electroless plating containing PdCl2 at 40 °C for 5 minutes, and then immersed in an electroless copper plating solution at 25 °C for 20 minutes. After annealing treatment by heating at 150 °C for 30 minutes, an etching resist was formed. After pattern formation by etching, electrolytic copper sulfate plating was performed to form a conductor layer with a thickness of 30 μm. Next, annealing treatment was performed at 200 °C for 60 minutes, and the obtained substrate was used as evaluation substrate B.

[0249] (4) Measurement of plating peel strength A cut with a width of 10 mm and a length of 100 mm was made in the conductor layer of evaluation substrate B, and one end of this was peeled off and grasped with a gripping tool (autocom type tester "AC-50C-SL" manufactured by T.S.E. Co., Ltd.). The load (kgf / cm) when peeling 20 mm vertically at a speed of 50 mm / min at room temperature was measured in accordance with JIS C6481.

[0250] <Measurement of Glass Transition Temperature and Dielectric Loss Tangent of Hardened Product> (1) Preparation of Hardened Product for Evaluation A PET film (manufactured by Lintec Corporation, "501010", thickness 50 μm, 240 mm square) having a treated surface with a release treatment and an untreated surface without a release treatment was prepared. On the untreated surface of this PET film, a glass cloth base epoxy resin double-sided copper-clad laminate (manufactured by Panasonic Corporation, "R5715ES", thickness 0.7 mm, 255 mm square) was overlaid, and the four sides were fixed with a polyimide adhesive tape (width 10 mm).

[0251] Subsequently, the resin varnishes manufactured in the examples and comparative examples were applied onto the treated surface of the PET film with a die coater so that the thickness of the resin composition layer after drying was 40 μm, and dried at 80°C to 120°C (average 100°C) for 10 minutes to obtain a resin sheet. Next, after being put into an oven at 190°C, the resin composition layer was thermally cured under the curing conditions for 90 minutes. After thermal curing, the polyimide adhesive tape was peeled off, the glass cloth base epoxy resin double-sided copper-clad laminate was removed, and further the PET film was peeled off to obtain a sheet-like hardened product. The obtained hardened product was referred to as the "hardened product for evaluation".

[0252] (2) Measurement of Glass Transition Temperature The hardened product for evaluation was cut to obtain a test piece having a width of about 5 mm and a length of about 15 mm. For this test piece, thermomechanical analysis was performed by the tensile loading method using a thermomechanical analyzer (manufactured by Rigaku Corporation, "Thermo Plus TMA8310"). Specifically, after mounting the test piece on the thermomechanical analyzer, measurements were continuously performed twice under the measurement conditions of a load of 1 g and a heating rate of 5°C / min. Then, in the second measurement, the glass transition temperature Tg (°C) was calculated.

[0253] (3) Measurement of Dielectric Loss Tangent The cured product for evaluation was cut into pieces with a length of 80 mm and a width of 2 mm to obtain evaluation samples. For these evaluation samples, the relative permittivity was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C by the cavity resonance perturbation method using an HP8362B device manufactured by Agilent Technologies. Measurements were performed on two test pieces, and the average value was calculated.

[0254] <Calculation of biomass ratio> According to the definition of the Japan Organic Resources Association, "biomass" refers to renewable organic resources derived from organisms excluding fossil resources (however, it includes inorganic resources such as shells directly produced by organisms). Based on this definition, the biomass ratio of the raw materials used in the formulation was calculated using the following formula. Biomass ratio (mass%) = (weight of bio-derived components in the substance / weight of the substance) × 100

[0255]

Table 1

Table 2

Claims

1. (A) A compound represented by the following formula (A-1), (B) A thermosetting resin, and (C) An inorganic filler, and contains (B) The thermosetting resin is an epoxy resin-containing resin composition. 【Chemical Formula 1】 (In formula (A-1), R １ and R ２ each independently represents a monovalent aromatic group which may have a substituent, X each independently represents an oxygen atom or a sulfur atom, A each independently represents any one group selected from the group represented by the following formula (A-2) and formula (A-3), n represents the number of repetitions and satisfies 0 ≦ n ≦ 8.) 【Chemical Formula 2】 (In formula (A-2), R １１ and R １２ each independently represents a divalent aromatic group which may have a substituent, L １１ each independently represents a single bond or a divalent linking group which may have a substituent, R １１ and L １１ may combine together to form a ring. a represents a number in the range of 0 to 5.) 【Chemical Formula 3】 (In formula (A-3), R １３ and R １４ each independently represents a divalent aromatic group which may have a substituent, L １２ represents a group represented by formula (A-4). b and c each independently represent a number in the range of 0 to 5.) 【Chemical Formula 4】 (In formula (A-4), R １５ and R １６ each independently represents a divalent aromatic group which may have a substituent, L １３ each independently represents a single bond or a divalent linking group which may have a substituent, R １５ and L １３ may combine together to form a ring. d represents a number in the range of 0 to 5.) **Claim 2** In formula (A-1), R １ and R ２ each independently represents a phenyl group which may have a substituent, or a naphthyl group which may have a substituent. The resin composition according to claim 1. **Claim 3** In formula (A-2) and formula (A-3), R １１ , R １２ , R １３ , and R １４ each independently represents a phenylene group which may have a substituent, or a naphthylene group which may have a substituent. The resin composition according to claim 1. **Claim 4** In formula (A-4), R １５ , and R １６ each independently represents a phenylene group which may have a substituent, or a naphthylene group which may have a substituent. The resin composition according to claim 1. **Claim 5** In formula (A-2), L １１ each independently represents a single bond, a divalent aliphatic group which may have a substituent, an oxygen atom, a divalent aromatic group which may have a substituent, a carbonyl group, or a sulfonyl group. The resin composition according to claim 1. **Claim 6** In formula (A-2), L １１ each independently represents a single bond, a divalent aliphatic group which may have a substituent, an oxygen atom, a phenylene group, a fluorenylidene group, a carbonyl group, or a sulfonyl group. The resin composition according to claim 1. **Claim 7** The resin composition according to claim 1, wherein X in formula (A-1) represents an oxygen atom.

8. The resin composition according to claim 1, wherein X in formula (A-1) represents a furan skeleton having an oxygen atom, carbonyl groups are bonded to the 2-position and 5-position of the furan skeleton, and the biomass ratio of the compound is 10% by mass or more.

9. The resin composition according to claim 1, wherein X in formula (A-1) represents a sulfur atom.

10. The resin composition according to claim 1, wherein A in formula (A-1) represents any one group selected from the groups represented by the following formulas (1a) to (4a). 【Chemical formula 5】 (In the formula, a1 represents a number in the range of 0 to 4, b1 and c1 each independently represent a number in the range of 0 to 5. "*" represents a bond.)

11. The resin composition according to claim 1, wherein the number average molecular weight of component (A) is 5000 or less.

12. The resin composition according to claim 1, wherein the active group equivalent of component (A) is 100 g / eq. or more.

13. The resin composition according to claim 1, which is for forming an insulating layer.

14. A resin sheet including a support and a resin composition layer provided on the support and containing the resin composition according to any one of claims 1 to 13.

15. A printed wiring board including an insulating layer formed of a cured product of the resin composition according to any one of claims 1 to 13.

16. A semiconductor device including the printed wiring board according to claim 15.

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