KR20240076733A - Compound - Google Patents

Abstract

[Project] Providing compounds that form cured products with a high glass transition temperature (Tg).
[Solution] A compound represented by formula (A-1).

[Representative] None

Description

Compound {COMPOUND}

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

An insulating layer is generally provided on a printed wiring board, 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.

Japanese Patent Publication No. 2019-66792

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.

The object of the present invention is to provide a compound that forms a cured product with a high glass transition temperature (Tg); A resin composition containing the above compound; a resin sheet including a resin composition layer containing the resin composition; a printed wiring board including an insulating layer formed from a cured product of the resin composition; and, a semiconductor device including the printed wiring board; The purpose is to provide.

As a result of intensive studies to solve the above problems, the present inventor discovered that the above problems could be solved by a compound having a predetermined structure, and thus completed the present invention.

That is, the present invention includes the following.

[1] A compound represented by the following formula (A-1).

(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 formulas (A-2) and (A-3),

n represents the number of repetitions and satisfies 0≤n≤8)

(In formula (A-2),

R ¹¹ and R ¹² each independently represent a divalent aromatic group that may have a substituent,

L ¹¹ each independently represents a single bond or a divalent linking group that may have a substituent, and R ¹¹ and L ¹¹ may combine as one to form a ring.

a represents a number ranging from 0 to 5)

(In formula (A-3),

R ¹³ and R ¹⁴ each independently represent a divalent aromatic group that may have a substituent,

L ¹² represents a group represented by formula (A-4).

b and c each independently represent a number ranging from 0 to 5)

(In formula (A-4),

R ¹⁵ and R ¹⁶ each independently represent a divalent aromatic group that may have a substituent,

L ¹³ each independently represents a single bond or a divalent linking group that may have a substituent, and R ¹⁵ and L ¹³ may combine as one to form a ring.

d represents a number ranging from 0 to 5)

[2] The compound according to [1], wherein R ¹ and R ² in formula (A-1) each independently represent a phenyl group which may have a substituent, or a naphthyl group which may have a substituent.

[3] R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ in formulas (A-2) and (A-3) are each independently a phenylene group which may have a substituent, or a phenylene group which may have a substituent. The compound according to [1] or [2], which represents a naphthylene group.

[4] In formula (A-4), R ¹⁵ and R ¹⁶ each independently represent any of [1] to [3], which represents a phenylene group which may have a substituent or a naphthylene group which may have a substituent. Compounds described in one.

[5] L ¹¹ in formula (A-2) is 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 sulfonyl. The compound according to any one of [1] to [4], which represents a group.

[6] L ¹¹ in formula (A-2) each independently represents a single bond, a divalent aliphatic group that may have a substituent, an oxygen atom, a phenylene group, a fluolenylidene 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] In formula (A-1), The compound according to any one of [1] to [7].

[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 the formula (A-1) represents one or more groups selected from groups represented by the following formulas (1a) to (4a).

(In the formula, a1 represents a number in the range of 0 to 4, and b1 and c1 each independently represent a number in the range of 0 to 5. “*” represents a bond.)

[11] The compound according to any one of [1] to [10], wherein the compound has a number average molecular weight of 5000 or less.

[12] The compound according to any one of [1] to [11], wherein the active group equivalent is 100 g/eq. or more.

[13] (A) The compound according to any one of [1] to [12],

(B) thermosetting resin, and

(C) A resin composition containing an inorganic filler.

[14] The resin composition according to [13], for forming an insulating layer.

[15] A resin sheet comprising 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 comprising 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].

According to the present invention, a compound forming a cured product with a high glass transition temperature (Tg); A resin composition containing the above compound; a resin sheet including a resin composition layer containing the resin composition; a printed wiring board including an insulating layer formed from a cured product of the resin composition; And a semiconductor device including the printed wiring board can be provided.

1 is a GPC chart of polyester resin (1).
Figure 2 is an IR chart of polyester resin (1).
Figure 3 is a GPC chart of polyester resin (2).
Figure 4 is an IR chart of polyester resin (2).
Figure 5 is a GPC chart of polyester resin 16.
Figure 6 is an IR chart of polyester resin 16.
Figure 7 is a GPC chart of polyester resin (17).
Figure 8 is an IR chart of polyester resin (17).
Figure 9 is a GPC chart of polyester resin (18).
Figure 10 is an IR chart of polyester resin 18.

Hereinafter, the present invention will be described by showing embodiments and examples. However, the present invention is not limited to the embodiments and examples shown below, and may be implemented with any modification without departing from the scope of the claims and equivalents of the present invention.

In this specification, the term “may have a substituent” referring to a compound or group means that the hydrogen atom of the compound or group is not substituted by a substituent, and some or all of the hydrogen atoms of the compound or group are substituted by a substituent. It means both sides when replaced with .

In this specification, unless otherwise specified, “substituent” refers to a halogen atom, alkyl group, cycloalkyl group, alkoxy group, alkenyl group, cycloalkyloxy group, aryl group, aryloxy group, arylalkyl group, arylalkoxy group, monovalent group. It refers to heterocyclic group, alkylidene group, amino group, silyl group, acyl group, acyloxy group, carboxy group, sulfo group, cyano group, nitro group, hydroxy group, mercapto group and oxo group.

Examples of halogen atoms used as substituents include fluorine atom, chlorine atom, bromine atom, and iodine atom.

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

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

The alkoxy group used as a substituent may be either linear or branched. The number of carbon atoms of the alkoxy group is preferably 1 to 20, more preferably 1 to 12, and still more preferably 1 to 6. Examples of the alkoxy group include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group, sec-butoxy group, isobutoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, and hepyloxy group. Examples include tyloxy group, octyloxy group, nonyloxy group, and decyloxy group.

The alkenyl group used as a substituent is a monovalent unsaturated hydrocarbon group having one carbon-carbon double bond, and may be linear or branched. The number of carbon atoms of 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 vinyl, allyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, and decenyl.

The number of carbon atoms of 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 cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, and cyclohexyloxy group.

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

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

The number of carbon atoms of the arylalkyl group used as a substituent is preferably 7 to 25, more preferably 7 to 19, even more preferably 7 to 15, and even more preferably 7 to 11. Examples of the arylalkyl group include phenyl-C ₁ to C ₁₂ alkyl group, naphthyl-C ₁ to C ₁₂ alkyl group, and anthracenyl-C ₁ to C ₁₂ alkyl group.

The number of carbon atoms of the arylalkoxy group used as a substituent is preferably 7 to 25, more preferably 7 to 19, even more preferably 7 to 15, and even more preferably 7 to 11. Examples of the arylalkoxy group include phenyl-C ₁ to C ₁₂ alkoxy group and naphthyl-C ₁ to C ₁₂ alkoxy group.

A monovalent heterocyclic group used as a substituent refers to a group in which one hydrogen atom has been removed from the heterocyclic ring 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 also includes a monovalent aromatic heterocyclic group (heteroaryl group). Examples of the monovalent heterocycle include thienyl group, pyrrolyl group, furanyl group, furyl group, pyridyl group, pyridazinyl group, pyrimidyl group, pyrazinyl group, triazinyl group, pyrrolidyl group, and piperidyl group. , quinolyl group, and isoquinolyl group.

An 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 of the alkylidene group is preferably 1 to 20, more preferably 1 to 14, even more preferably 1 to 12, even more preferably 1 to 6, and particularly preferably 1 to 3. Examples of the alkylidene group include methylidene group, ethylidene group, propylidene group, isopropylidene group, butylidene group, sec-butylidene group, isobutylidene group, tert-butylidene group, and pentylidene group. , hexylidene group, heptylidene group, octylidene group, nonylidene group, and decylidene group.

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 phenyl group, naphthyl group, and anthracenyl group. The number of carbon atoms of the acyl group is preferably 2 to 20, more preferably 2 to 13, and even more preferably 2 to 7. Examples of the acyl group include acetyl group, propionyl group, butyryl group, isobutyryl group, pivaloyl group, and benzoyl group.

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 phenyl group, naphthyl group, and anthracenyl group. The number of carbon atoms of 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 acetoxy group, propionyloxy group, butyryloxy group, isobutyryloxy group, pivaloyloxy group, and benzoyloxy group.

The above-mentioned substituent may further have a substituent (hereinafter sometimes referred to as a “secondary substituent”). As the secondary substituent, unless otherwise specified, the same substituent as the above-mentioned substituent may be used.

[compound]

The compound of the present invention is represented by the following formula (A-1).

(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 formulas (A-2) and (A-3),

n represents the number of repetitions and satisfies 0≤n≤8)

(In formula (A-2),

R ¹¹ and R ¹² each independently represent a divalent aromatic group that may have a substituent,

L ¹¹ each independently represents a single bond or a divalent linking group that may have a substituent, and R ¹¹ and L ¹¹ may combine as one to form a ring.

a represents a number ranging from 0 to 5)

(In formula (A-3),

R ¹³ and R ¹⁴ each independently represent a divalent aromatic group that may have a substituent,

L ¹² represents a group represented by formula (A-4).

b and c each independently represent a number ranging from 0 to 5)

(In formula (A-4),

R ¹⁵ and R ¹⁶ each independently represent a divalent aromatic group that may have a substituent,

L ¹³ each independently represents a single bond or a divalent linking group that may have a substituent, and R ¹⁵ and L ¹³ may combine as one to form a ring.

d represents a number ranging from 0 to 5)

The compound of the present invention can form a cured product with a high glass transition temperature (Tg). Hereinafter, the compounds of the present invention will be described in detail.

In formula (A-1), R ¹ and R ² each independently represent a monovalent aromatic group that may have a substituent. A monovalent aromatic group refers to a group in which one hydrogen atom has been removed from the aromatic ring of an aromatic compound, and an “aromatic ring” is a group according to Hückel's rule in which the number of electrons contained in the cyclic π electron system is 4n+2 (n is a natural number). refers to a ring, 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 that may have a substituent include an aryl group that may have a substituent, and a heteroaryl group that 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, and even more preferably 6 or more, and the upper limit is preferably 24 or less, more preferably 18 or less or 14. or less, more preferably 10 or less. The number of carbon atoms of the substituent is not included in the number of carbon atoms.

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 with 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, and 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, the monovalent aromatic group represented by R ¹ and R ² 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. A phenyl group or a naphthyl group which may have a substituent is more preferable, and a naphthyl group which may have a substituent is even more preferable.

In formula (A-1), X each 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 with carbonyl groups bonded at the 2- and 5-positions, or a thiophene skeleton with carbonyl groups bonded with the 2- and 5-positions.

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

In formula (A-2), R ¹¹ and R ¹² each independently represent a divalent aromatic group that may have a substituent. A divalent aromatic group refers to a group in which two hydrogen atoms have been removed from the aromatic ring of an aromatic compound. Examples of the divalent aromatic group that may have a substituent include an arylene group that may have a substituent and a heteroarylene group that 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, and even more preferably 6 or more, and the upper limit is preferably 30 or less, more preferably 24 or less, and further preferably 30 or less. Preferably it is 18 or less or 14 or less, particularly preferably 10 or less. The number of carbon atoms of the substituent is not included in the number of carbon atoms. In a suitable embodiment, the divalent aromatic group represented by R ¹¹ and R ¹² is a phenylene group which may have a substituent; Naphthylene group which may have a substituent; Phenylene group-fluolenylidene group-phenylene group, which may have a substituent; Biphenylene group which may have a substituent; More preferably, it is 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 suitable. 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.

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

Examples of the divalent aliphatic group in L ¹¹ include alkylene group, cycloalkylene group, alkenylene group, cycloalkenylene group, and alkapolyeneylene group (the number of double bonds is preferably 2 to 10, more preferably Examples include 2 to 6, more preferably 2 to 4, even more preferably 2), etc., and alkylene groups, cycloalkylene groups, alkenylene groups, and cycloalkenylene groups are preferable, and alkylene groups and cycloalkyl groups are preferable. A lene group is more preferable, and a cycloalkylene group is still more preferable.

The alkylene group in L ¹¹ may be either linear or branched, and its number of carbon atoms is preferably 1 to 12, more preferably 1 to 6, and still 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 methylene group, ethylene group, propylene group, 2-propylene group, 1,1-dimethyl-3-methylpropylene group, butylene group, pentylene group, and hexylene group.

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

The alkenylene group in L ¹¹ may be linear or branched, and its number of 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 ethenylene group, propenylene group, butenylene group, pentenylene group, and hexenylene group.

The number of carbon atoms of the cycloalkenylene group in L ¹¹ is preferably 3 to 15, more preferably 3 to 12, and still 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 cyclopropenylene group, cyclobutenylene group, cyclopentenylene group, cyclohexenylene group, and norbornenylene group.

Examples of the divalent aromatic group in L ¹¹ include an arylene group and a heteroarylene group, with an arylene group being preferable.

The number of carbon atoms of the arylene group in L ¹¹ 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 phenylene group, naphthylene group, anthracenylene group, fluorenediyl group (for example, 9H-fluorene-9,9-diyl group), fluorenenylidene group, phenanthrenediyl group, and indane. A diyl group, a pyrenediyl group, etc. are mentioned, and a phenylene group and a fluolenylidene group are preferable.

The number of carbon atoms of the heteroarylene group in L ¹¹ 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 heteroarylene groups include pyrrole diyl group, furandiyl group, thiophene diyl group, pyridine diyl group, pyridazine diyl group, pyrimidine diyl group, pyrazine diyl group, triazine diyl group, piperidine diyl group, and triazole diyl group. Examples include diyl group, purindiyl group, carbazole diyl group, quinoline diyl group, and isoquinoline diyl group.

R ¹¹ and L ¹¹ may be combined as one 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 the formula (A-2) is 1, R ¹¹ and L ¹¹ are preferably combined to form a ring. On the other hand, when R ¹¹ and L ¹¹ are combined as one to form a ring, it is preferable that a phenylene group and a cyclopentylene group are combined to form an indan ring.

As L ¹¹ , from the viewpoint of forming a cured product with a high glass transition temperature (Tg), each independently represents a single bond, a divalent aliphatic group that may have a substituent, an oxygen atom, a divalent aromatic group that may have a substituent, It is preferable to represent a carbonyl group and a sulfonyl group, and each independently represents a single bond, a divalent aliphatic group that may have a substituent, an oxygen atom, a phenylene group, a fluolenylidene group, a carbonyl group, or a sulfonyl group. Preferred, 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, or a cycloalkylene group having 3 to 15 carbon atoms which may have a substituent, or a substituent. An arylene group having 6 to 24 carbon atoms, which may have a substituent, is preferable, and a cycloalkylene group having 3 to 15 carbon atoms, which may have a substituent, is more preferable.

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. On the other hand, when a is 1, R ¹¹ and L ¹¹ may be combined to form a ring.

In formula (A-3), R ¹³ and R ¹⁴ each independently represent a divalent aromatic group that 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 one preferred embodiment, the divalent aromatic group represented by R ¹³ and R ¹⁴ is a phenylene group which may have a substituent, 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 preferable and a methyl group is more preferable as the substituent.

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

In formula (A-4), R ¹⁵ and R ¹⁶ each independently represent a divalent aromatic group that may have a substituent. The divalent aromatic is the same as the divalent aromatic group represented by R ¹¹ in formula (A-2). In one preferred embodiment, the divalent aromatic group represented by R ¹⁵ and R ¹⁶ 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. am. When the divalent aromatic group has a substituent, an alkyl group is preferable and a methyl group is more preferable as the substituent.

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

In formula (A-4), d represents a number in the range of 0 to 5, and 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 be combined to form a ring, and it is preferable that they form a ring, especially when d is 1.

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

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 groups represented by formulas (1a) to (4a) are preferable. 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, and "*" represents a bond. a1 is the 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). In addition, in the group represented by formula (13a), d and e each represent an integer of 0 to 4, and satisfy 1≤d+e≤4.

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, preferably 7 or less, more preferably 6 or less, and even more preferably 5 or less.

As a suitable 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 each independently represent 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 that may have a substituent, or a divalent aromatic group that may have a substituent,

In formula (A-2), a represents a number in the range of 0 to 5, and when a is 1, R ¹¹ and L ¹¹ may become one and combine to form a ring.

In formula (A-3), R ¹³ and R ¹⁴ are phenylene groups which may have substituents,

L ¹² is a group represented by formula (A-4),

In formula (A-4), R ¹⁵ and R ¹⁶ are phenylene groups which may have substituents,

In formula (A-4), L ¹³ is a divalent aliphatic group that may have a substituent,

In formula (A-4), d represents a number ranging from 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.

Specific examples of the compounds of the present invention include the following compounds (1) to (18). However, the compound is not limited to these specific examples. In the formula, n is 0≤n≤8, and a, b, and c represent numbers ranging from 0 to 5. d and e each represent an integer from 0 to 4, and satisfy 1≤d+e≤4.

The number average molecular weight (Mn) of the compound of the present invention is preferably 5000 or less, more preferably 4000 or less, and still more preferably 3000 or less, from the viewpoint of forming a cured product with a high glass transition temperature (Tg), Preferably it is 100 or more, more preferably 500 or more, and even 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.

The molecular weight distribution (Mw/Mn) of the compound of the present invention is preferably 2 or less, more preferably 1.8 or less, and still more preferably 1.5 or less from the viewpoint of forming a cured product with a high glass transition temperature (Tg). , preferably 0.5 or more, more preferably 0.7 or more, and even more preferably 1.0 or more.

The active group equivalent (active ester group equivalent) of the compound of the present invention is preferably 100 g/eq from the viewpoint of forming a cured product with a high glass transition temperature (Tg). or more, more preferably 120 g/eq. or more, more preferably 130 g/eq. or more, preferably 1000 g/eq. or less, more preferably 750 g/eq. or less, and even more preferably 300 g/eq. It is as follows. The active group equivalent is the mass of the compound of the present invention containing 1 equivalent of the active group.

The compounds of the present invention are preferably synthesized using plant-derived raw materials from the viewpoints of energy saving, cost reduction, and environmental conservation. For example, compounds having a furan ring can be derived from biomass such as plant-derived glucose, plant-derived cellulose, and plant-derived fructose. Such compounds having a furan ring derived from biomass are, for example, compounds in which a carbonyl group is bonded to the 2nd and 5th positions of the furan skeleton, and specifically, they are 2,5-furandicarboxylic acid and the like. 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 a skeleton of a compound having a furan ring derived from biomass, the compound of the present invention has the formula (A-1) is an embodiment in which X is an oxygen atom and has a furan skeleton with carbonyl groups bonded to the 2nd and 5th positions.

The biomass ratio of the compound of the present invention is preferably 10 mass% or more, more preferably 15 mass% or more, and even more preferably 20 mass% or more from the viewpoint of reducing the environmental load. The upper limit is not particularly limited, but is preferably 100 mass% or less, more preferably 75 mass% or less, and even more preferably 50 mass% or less, 30 mass% or less, and 10 mass% or less. The biomass ratio is the ratio of biomass-derived components contained in the compound, and can be specifically measured by the method described in the Examples described later. Even if the compound of the present invention is a compound that has been certified by the mass balance method, the biomass ratio of the compound of the present invention is calculated by the method described in the Examples described later.

The compounds of the present invention are

1) A hydroxyl group-containing aromatic compound having an aromatic hydroxyl group,

2) dicarboxylic acid halides having a furan skeleton or a thiophene skeleton, and

3) Divalent phenolic compounds

It can be obtained by carrying out a condensation reaction.

A 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 may constitute R ¹ and R ² in formula (A-1). Examples of such compounds include 1-naphthol, phenol, orthophenylphenol, isobornylphenol, cardanol, and eugenol.

A 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 using a compound having a furan ring derived from biomass, the compound having a furan ring derived from biomass may be chlorinated and then used as a raw material for the compound of the present invention.

A divalent phenol compound is a compound in which a dicarboxylic acid halide having a furan skeleton or a thiophene skeleton and the phenol moiety of the compound can react, and can constitute A of the formula (A-1). Such compounds include dicyclopentadiene-phenol polyadduct, 4,4'-(9-fluorenylidene)diphenol, 4,4'-dihydroxydiphenyl ether, and 4,4'-dihydroxy. Benzophenone, bisphenol A, bisphenol F, 2,2'-diallylbisphenol A, bisphenol S, 4,4'-dihydroxybiphenyl, 2,7-naphthalenediol, daidzein, etc. Additionally, commercially available divalent phenol compounds may be used. Commercially available products include, for example, “J-DPP85” manufactured by JFE Chemicals and “SA90” manufactured by SABIC Innovative Plastics.

In the condensation reaction, a phase transfer catalyst such as tetra-n-butylammonium bromide may be used as needed. As the phase transfer catalyst, any conventionally known catalyst that can be used in an esterification reaction may be used. Additionally, 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; and tertiary amines such as triethylamine, pyridine, and N,N-diisopropylethylamine. Bases may be used individually or in combination of two or more types.

In addition, the condensation reaction may be carried out in a solvent-free system without using a solvent, or may be carried out in an organic solvent system using an organic solvent. Examples of organic solvents include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate. Acetic acid ester-based solvent; carbitol-based solvents such as cellosolve and butyl carbitol; Aromatic hydrocarbon solvents such as toluene and xylene; Amide-based solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone can be mentioned. Organic solvents may be used individually, or may be used in combination of two or more types.

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

After completion of the reaction, if necessary, a purification process such as water washing or microfiltration may be performed to remove by-product salts and excess starting materials from the system. In detail, the amount of water necessary to dissolve the by-product salt is added and stirred, and then the water layer is removed. Thereafter, the organic layer is dried and, if necessary, the organic solvent is distilled off to obtain the compound of the present invention. It may be used as a solvent for the resin composition without completely removing the organic solvent.

[Resin composition]

The resin composition of the present invention includes (A) the compound of the present invention, (B) a thermosetting resin, and (C) an inorganic filler. According to this resin composition, it becomes possible to obtain a cured product with a high glass transition temperature. Additionally, it is usually possible to obtain a cured product with high peel strength and low dielectric loss tangent.

The resin composition is prepared by combining (A) the compound of the present invention, (B) a thermosetting resin, and (C) an inorganic filler, (D) a radical polymerizable resin, (E) a curing accelerator, (F) an organic filler, (G) ) Thermoplastic resin, and (H) other additives may be included.

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

When the epoxy group number of the epoxy resin as component (B) is 1, the active group number of component (A) is preferably 0.01 or more, more preferably 0.05 or more, from the viewpoint of significantly obtaining the effect of the present invention. Typically, it is 0.1 or more, preferably 5 or less, more preferably 3 or less, and even more preferably 1 or less. “The epoxy group number of the epoxy resin” refers to the sum of all 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. In addition, “the number of active groups of component (A)” refers to the sum of all the values obtained by dividing the mass of the non-volatile component of component (A) present in the resin composition by the active group equivalent.

The content of component (A) is preferably 1% by mass or more, more preferably 3% by mass or more, when the non-volatile component of the resin composition is 100% by mass, from the viewpoint of significantly obtaining the effect of the present invention. Preferably it is 5 mass% or more, preferably 40 mass% or less, more preferably 30 mass% or less, and even more preferably 20 mass% or less. Meanwhile, unless otherwise specified, the content of each component in the resin composition is a value assuming that the non-volatile component in the resin composition is 100% by mass, and the non-volatile component refers to the entire non-volatile component in the resin composition excluding the solvent. it means.

<(B) Thermosetting resin>

The resin composition contains (B) thermosetting resin as component (B). (B) The type of thermosetting resin is not particularly limited as long as it can be cured in combination with component (A). The thermosetting resin (B) as this component (B) does not include the component corresponding to the component (A) described above. (B) Thermosetting resin may be used individually or in combination of two or more types.

Examples of thermosetting resins include epoxy resins, phenol resins, cyanate resins, activated ester resins, carbodiimide resins, acid anhydride resins, amine resins, benzoxazine resins, and thiol resins. Thermosetting resins may be used individually or in combination of two or more types. Among these, the thermosetting resin preferably contains at least one type selected from the group consisting of epoxy resin, phenol resin, and cyanate resin.

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 that can cure the resin composition by reacting with the epoxy resin. A resin that can react with an epoxy resin and harden the resin composition may hereinafter be referred to as a “curing agent.” Examples of the curing agent include phenol resin, cyanate resin, activated ester resin, carbodiimide resin, acid anhydride resin, amine resin, benzoxazine resin, and thiol resin. Among these, the curing agent preferably contains at least one type selected from the group consisting of phenol resin and cyanate resin. One type of hardening agent may be used individually, or two or more types may be used in combination.

Epoxy resin is a thermosetting resin having an epoxy group. As epoxy resins, for example, bixylenol 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, trisphenol type epoxy resin. Resin, naphthol novolac 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 Di-ester type epoxy resin, cresol novolak type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin with 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, phenolphthalimidine type epoxy resin. etc. can be mentioned. Epoxy resins may be used individually or in combination of two or more types.

(A) The thermosetting resin is an epoxy resin, and preferably contains an epoxy resin having two or more epoxy groups in one molecule. The proportion of the epoxy resin having two or more epoxy groups per molecule relative to 100% by mass of the non-volatile component of the epoxy resin is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass. That's it.

Epoxy resins include epoxy resins that are liquid at a temperature of 20°C (hereinafter sometimes referred to as “liquid epoxy resins”) and epoxy resins that are solid at a temperature of 20°C (hereinafter sometimes referred to as “solid epoxy resins”). There is. The resin composition may contain only a liquid epoxy resin as an epoxy resin, may contain only a solid epoxy resin, or may contain a combination of a liquid epoxy resin and a solid epoxy resin.

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

Liquid epoxy resins include bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol AF-type epoxy resin, naphthalene-type epoxy resin, glycidyl ester-type epoxy resin, glycidylamine-type epoxy resin, and phenol novolak-type epoxy resin. , alicyclic epoxy resins having an ester skeleton, cyclohexane-type epoxy resins, cyclohexanedimethanol-type epoxy resins, and epoxy resins having a butadiene structure are preferable, and bisphenol A-type epoxy resins and naphthalene-type epoxy resins are more preferable.

Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", and "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) manufactured by Mitsubishi Chemical Corporation epoxy resin); "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; “630”, “630LSD”, and “604” (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; “ED-523T” manufactured by ADEKA (glycirol type epoxy resin); “EP-3950L” and “EP-3980S” (glycidylamine type epoxy resin) manufactured by ADEKA; “EP-4088S” manufactured by ADEKA (dicyclopentadiene type epoxy resin); “ZX1059” manufactured by Nittetsu Chemical & Materials Co., Ltd. (mixture of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin); “EX-721” (glycidyl ester type epoxy resin) manufactured by Nagase Chemtex Corporation; “Celoxide 2021P” manufactured by Daicel Corporation (alicyclic epoxy resin with an ester skeleton); “PB-3600” manufactured by Daicel Corporation, “JP-100” and “JP-200” manufactured by Nippon Soda Corporation (epoxy resin (epoxidized polybutadiene resin) having a butadiene structure); “ZX1658” and “ZX1658GS” (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nittetsu Chemical & Materials. These may be used individually or in combination of two or more types.

As a solid epoxy resin, a solid epoxy resin having 3 or more epoxy groups per molecule is preferable, and an aromatic solid epoxy resin having 3 or more epoxy groups per molecule is more preferable.

As solid epoxy resins, xylenol-type epoxy resin, naphthalene-type epoxy resin, naphthalene-type tetrafunctional epoxy resin, naphthol novolak-type epoxy resin, cresol novolak-type epoxy resin, dicyclopentadiene-type epoxy resin, and ttolysphenol-type epoxy. Resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, phenol aralkyl type epoxy resin, tetraphenylethane type epoxy resin, Phenolphthalimidine type epoxy resin is preferable, and biphenyl type epoxy resin and naphthylene ether type epoxy resin are more preferable.

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 novolac type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "HP-7200", "HP-7200HH", "HP-7200H", and "HP-7200L" (dicyclopentadiene type epoxy 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” manufactured by Nippon Kayaku Co., Ltd. (trisphenol type epoxy resin); “NC7000L” manufactured by Nippon Kayaku Co., Ltd. (naphthol novolac type epoxy resin); "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 Nittetsu Chemical & Materials Co., Ltd.; “ESN485” (naphthol type epoxy resin) manufactured by Nittetsu Chemical &Materials; “ESN375” (dihydroxynaphthalene type epoxy resin) manufactured by Nittetsu Chemical &Materials; "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" (phenolphthalimidine type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., etc. are mentioned. These may be used individually or in combination of two or more types.

As an epoxy resin, when using a combination of liquid epoxy resin and solid 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, especially preferably 1:0.1 to 1:7.

The epoxy equivalent weight of the epoxy resin is preferably 50 g/eq. to 5,000 g/eq., more preferably 60 g/eq. to 3,000 g/eq., more preferably 80 g/eq. to 2,000 g/eq., particularly preferably 110 g/eq. to 1,000 g/eq. Epoxy equivalent represents the mass of resin per equivalent of epoxy group. This epoxy equivalent can be measured according to JIS K7236.

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).

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

As the phenol resin, a compound having one or more, preferably two or more, hydroxyl groups bonded to an aromatic ring such as a benzene ring or naphthalene ring per molecule can be used. When a phenol resin is combined with an epoxy resin, it reacts with the epoxy resin and can harden the resin composition, so it is sometimes referred to as a “phenol-based curing agent.” The phenol resin is preferably a phenol resin having a novolac structure from the viewpoint of significantly obtaining the effects of the present invention. Furthermore, from the viewpoint of adhesion, a nitrogen-containing phenol resin is preferable, and a triazine skeleton-containing phenol resin is more preferable. Among them, a phenol novolak resin containing a triazine skeleton is preferable from the viewpoint of significantly obtaining the effects of the present invention. Specific examples of the phenol resin include, for example, "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., and "NHN", "CBN", and "GPH" manufactured by Nippon Kayaku Co., Ltd. ”, “SN-170”, “SN-180”, “SN-190”, “SN-475”, “SN-485”, “SN-495”, “SN-375” manufactured by Nittetsu Chemical & Materials Co., Ltd. ”, “SN-395”, “LA-7052”, “LA-7054”, “LA-3018”, “LA-3018-50P”, “LA-1356”, “TD2090”, “TD” manufactured by DIC Corporation -2090-60M”, “KA-1163”, etc.

As the cyanate resin, a compound having one or more, preferably two or more, cyanate groups in one molecule can be used. When cyanate resin is combined with an epoxy resin, it reacts with the epoxy resin and can harden the resin composition, so it is sometimes referred to as a “cyanate-based curing agent.” As cyanate resin, for example, bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate)), 4,4'-methylenebis (2,6-dimethyl phenylcyanate), 4,4'-ethylidenediphenyldicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanate) Natephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanate) Bifunctional cyanate resins such as phenyl)thioether and bis(4-cyanatephenyl)ether, polyfunctional cyanate resins derived from phenol novolak and cresol novolac, etc., and prepolymers in which these cyanate resins are partially triazinated. etc. can be mentioned. Specific examples of cyanate resins include "PT30" and "PT60" (both phenol novolak-type polyfunctional cyanate resins), "BA230", and "BA230S75" (all or part of bisphenol A dicyanate) manufactured by Lonza Japan. and prepolymers that have been triazinated into trimers).

Active ester resins generally include compounds having two or more highly reactive ester groups per molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. It is preferably used. When combined with an epoxy resin, the active ester resin can react with the epoxy resin and harden the resin composition, so 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. In particular, from the viewpoint of improving high-temperature reflow swelling resistance, active ester resins obtained from carboxylic acid compounds and hydroxy compounds are preferable, and active ester resins obtained from carboxylic acid compounds and phenol compounds and/or naphthol compounds are more preferable. Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. As phenol compounds or naphthol compounds, for example, hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, Trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, benzenetriol, dicyclopentadiene type diphenol compound, phenol novolac, etc. are mentioned. Here, “dicyclopentadiene-type diphenol compound” refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

Specifically, the active ester resin includes a dicyclopentadiene-type active ester resin, a naphthalene-type active ester resin containing a naphthalene structure, an active ester resin containing an acetylate of phenol novolac, and a benzoylate of phenol novolac. The following active ester resins are preferable, and among them, at least one type selected from dicyclopentadiene-type active ester resins and naphthalene-type active ester resins is more preferable. As the dicyclopentadiene type active ester resin, an active ester resin containing a dicyclopentadiene type diphenol structure is preferable.

Commercially available active ester resins include, for example, active ester resins containing a dicyclopentadiene-type diphenol structure, such as "EXB9451", "EXB9460", "EXB9460S", "EXB-8000L", and "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); As an active ester resin containing a naphthalene structure, “HP-B-8151-62T”, “EXB-8100L-65T”, “EXB-8150-60T”, “EXB-8150-62T”, and “EXB-9416-70BK” , “HPC-8150-60T”, “HPC-8150-62T”, “EXB-8” (manufactured by DIC); As a phosphorus-containing active ester resin, "EXB9401" (manufactured by DIC Corporation); As an activated ester resin which is an acetylate of phenol novolak, "DC808" (manufactured by Mitsubishi Chemical Corporation); Examples of active ester resins that are benzoylates of phenol novolak include "YLH1026", "YLH1030", and "YLH1048" (manufactured by Mitsubishi Chemical Corporation); Examples of the active ester resin containing a styryl group and a naphthalene structure include "PC1300-02-65MA" (manufactured by Airwater).

As the carbodiimide resin, a compound having one or more, preferably two or more, carbodiimide structures in one molecule can be used. When carbodiimide resin is combined with an epoxy resin, it reacts with the epoxy resin and can harden the resin composition, so it is sometimes referred to as a “carbodiimide-based curing agent.” Specific examples of carbodiimide resin include aliphatic biscarbodiimides such as tetramethylene-bis(t-butylcarbodiimide) and cyclohexanebis(methylene-t-butylcarbodiimide); Biscabodiimides such as aromatic biscabodiimides such as phenylene-bis(xylylcarbodiimide); Aliphatic polycarbodiimides such as polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylenecarbodiimide, poly(methylenebiscyclohexylenecarbodiimide), and poly(isophoronecarbodiimide). ; Poly(phenylenecarbodiimide), poly(naphthylenecarbodiimide), poly(tolylenecarbodiimide), poly(methyldiisopropylphenylenecarbodiimide), poly(triethylphenylenecarbodiimide), poly(di Ethylphenylenecarbodiimide), poly(triisopropylphenylenecarbodiimide), poly(diisopropylphenylenecarbodiimide), poly(xylylenecarbodiimide), poly(tetramethylxylylenecarbodiimide), poly (methylenediphenylenecarbodiimide), and aromatic polycarbodiimide such as poly[methylenebis(methylphenylene)carbodiimide]. Commercially available products of carbodiimide resin include, for example, "Carbodylight V-02B", "Carbodylight V-03", "Carbodylight V-04K", and "Carbodylight V-" manufactured by Nisshinbo Chemical Co., Ltd. 07" and "CarbodiLite V-09"; "Starbakusol P", "Starbakusol P400", and "Hycadyl 510" manufactured by Line Chemistry, etc.;

As the acid anhydride resin, a compound having one or more, preferably two or more, acid anhydride groups in one molecule can be used. When acid anhydride resin is combined with an epoxy group, it reacts with an epoxy resin and can harden the resin composition, so it is sometimes referred to as an “acid anhydride-based curing agent.” Specific examples of acid anhydride resin include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyl tetrahydrophthalic anhydride, Dodecenylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, trimellitic anhydride, pyromellitic anhydride, Benzophenone tetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride, naphthalenetetracarboxylic acid dianhydride, oxydiphthalic acid dianhydride, 3,3'-4,4'-diphenylsulfone tetracarboxylic acid 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(anhydro Trimellitate), polymeric acid anhydride such as styrene-maleic acid resin copolymerized with styrene and maleic acid, etc. are available as commercial products of acid anhydride resin, for example, “HNA-100” manufactured by Nippon Rika Corporation. ", "MH-700", "MTA-15", "DDSA", "OSA", "YH-306", "YH-307", manufactured by Resonac Corporation, "HN-2200", " MHAC-P"; "EF-30", "EF-40", "EF-60", and "EF-80" manufactured by Cray Vale.

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 the epoxy resin and harden 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, and aromatic amines. Among these, aromatic amines are preferable. The amine resin is preferably a primary amine or a secondary amine, and is more preferably a primary amine. Specific examples of amine resins include 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, and 3,3'-diaminodiphenylmethane. minodiphenyl sulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl , 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3- Dimethyl-5,5-diethyl-4,4-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. Examples of commercially available amine resins include "SEIKACURE-S" manufactured by Seika Corporation; "KAYABOND C-200S", "KAYABOND C-100", "Kayahard A-A", "Kayahard A-B", and "Kayahard A-S" manufactured by Nippon Kayaku Corporation; “Epicure W” manufactured by Mitsubishi Chemical Corporation; "DTDA" manufactured by Sumitomo Seika Co., Ltd., etc. are mentioned.

When benzoxazine resin is combined with an epoxy resin, it reacts with the epoxy resin and can harden the resin composition, so 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 Chemicals; “HFB2006M” manufactured by Showa Kobunshi Corporation; “P-d” and “F-a” manufactured by Shikoku Kaseiko Kogyo Co., Ltd. can be mentioned.

When a thiol resin is combined with an epoxy resin, it reacts with the epoxy resin and can harden the resin composition, so it is sometimes referred to as a “thiol-based curing agent.” Examples of thiol resins include trimethylolpropanetris(3-mercaptopropionate), pentaerythritoltetrakis(3-mercaptobutyrate), and tris(3-mercaptopropyl)isocyanurate. there is.

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., more preferably 100 g/eq. to 500 g/eq., particularly preferably 100 g/eq. to 300 g/eq. The active group equivalent is the mass of the curing agent per equivalent of the active group.

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 gel permeation chromatography (GPC).

When the epoxy group number of the epoxy resin is 1, the active group number of the curing agent is preferably 0.01 or more, more preferably 0.05 or more, further preferably 0.1 or more, preferably 5 or less, more preferably 3 or less, Particularly preferably, it is 2 or less. “Epoxy group number of an epoxy resin” refers to the sum of all 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. In addition, the “active group number of the curing agent” refers to the sum of all the values obtained by dividing the mass of the non-volatile component of the curing agent present in the resin composition by the active group equivalent.

(B) The content of the curing agent as a component is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, assuming that the non-volatile component in the resin composition is 100% by mass, from the viewpoint of significantly obtaining the effect of the present invention. , more preferably 0.5 mass% or more, preferably 20 mass% or less, more preferably 15 mass% or less, further preferably 10 mass% or less, 5 mass% or less, and 3 mass% or less.

(B) The content of the thermosetting resin is preferably 10.1% by mass or more, more preferably 10.3% by mass or more, assuming that the non-volatile component in the resin composition is 100% by mass, from the viewpoint of significantly obtaining the effects of the present invention. More preferably, it is 10.5 mass% or more, preferably 65 mass% or less, more preferably 60 mass% or less, even more preferably 55 mass% or less, 50 mass% or less, and 48 mass% or less.

<(C) Inorganic filler>

The resin composition contains (C) an inorganic filler as component (C). By containing component (C) in the resin composition, the dielectric loss tangent of the cured product can be reduced.

(C) As the material for the inorganic filler, an inorganic compound is used. (C) Inorganic filler materials include, for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, and hydroxide. Aluminum, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, Examples include barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Additionally, spherical silica is preferred as the silica. (C) Inorganic fillers may be used individually, or two or more types may be used in combination at any ratio.

(C) Commercially available inorganic fillers include, for example, “SP60-05” and “SP507-05” manufactured by Nittetsu Chemical &Materials; "YC100C", "YA050C", "YA050C-MJE", "YA010C", "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1" manufactured by Adomatex Corporation; “UFP-30”, “DAW-03”, and “FB-105FD” manufactured by Denka Corporation; “Silpen NSS-3N”, “Silpen NSS-4N”, and “Silpen NSS-5N” manufactured by Tokuyama Corporation; “Celpiers” and “MGH-005” manufactured by Taiheyo Cement Co., Ltd.; Examples include “Esperique” and “BA-1” manufactured by Nikki Shokubai Kasei.

(C) The inorganic filler may be an inorganic filler derived from biomass. Inorganic fillers derived from biomass are preferably manufactured from plant raw materials. For example, plants of the Horsetail and Poaceae families have the property of absorbing and accumulating silicon components in the ground. Therefore, by burning these plants, silica can be produced as combustion material (Patent No. 6389349). Inorganic fillers derived from biomass may be commercially available. Examples of commercially available inorganic fillers derived from biomass include “Esical Silica” manufactured by M.I.T., which is biomass silica manufactured from rice husk.

(C) The average particle diameter of the inorganic filler is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, further preferably 3 μm or less, even more preferably 2 μm or less, especially Preferably it is 1.5㎛ or less. (C) The lower limit of the average particle diameter of the inorganic filler is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, further preferably 0.1 μm or more, particularly preferably 0.2 μm or more. . (C) The average particle diameter of the inorganic filler can be measured by a laser diffraction/scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis using a laser diffraction/scattering type particle size distribution measuring device, and the median diameter can be measured as the average particle size. The measurement sample can be prepared by weighing 100 mg of inorganic filler and 10 g of methyl ethyl ketone into a vial bottle and dispersing them by ultrasonic waves for 10 minutes. For the measurement sample, use a laser diffraction type particle size distribution measuring device, use a light source wavelength of blue and red, measure the volume-based particle size distribution of the inorganic filler using a flow cell method, and determine the median diameter from the obtained particle size distribution. The average particle diameter was calculated as . Examples of the laser diffraction type particle size distribution measuring device include "LA-960" manufactured by Horiba Sesakusho Co., Ltd.

(C) The specific surface area of the inorganic filler is not particularly limited, but is preferably 0.1 m2/g or more, more preferably 0.5 m2/g or more, further preferably 1 m2/g or more, especially preferably 3. It is more than ㎡/g. (C) The upper limit of the specific surface area of the inorganic filler is not particularly limited, but is preferably 100 m2/g or less, more preferably 70 m2/g or less, even more preferably 50 m2/g or less, even more preferably Typically, it is 30 m2/g or less, particularly preferably 10 m2/g or less. The specific surface area of the inorganic filler can be obtained by adsorbing nitrogen gas to the surface of the sample using a specific surface area measuring device (Macsorb HM-1210, manufactured by Mountec) according to the BET method, and calculating the specific surface area using the BET multi-point method. there is.

(C) The inorganic filler is preferably treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Examples of surface treatment agents include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, and titanate coupling agents. Ringer, etc. can be mentioned. In addition, surface treatment agents may be used individually or in combination of two or more types.

Commercially available surface treatment agents include, for example, “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. and “KBM803” (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. silane), “KBE903” (3-aminopropyltriethoxysilane) manufactured by Shinetsu Chemical Co., Ltd., “KBM573” (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shinetsu Chemical Co., Ltd., Shinetsu Chemical Co., Ltd. “SZ-31” (hexamethyldisilazane) manufactured by Kogyo Co., Ltd., “KBM103” (phenyltrimethoxysilane) manufactured by Shinetsu Chemical Co., Ltd., “KBM-4803” (long-chain epoxy type silane couple) manufactured by Shinetsu Chemical Co., Ltd. ring agent), "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., etc.

The degree of surface treatment with a surface treatment agent is preferably within a predetermined range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, 100% by mass of the inorganic filler is preferably surface treated with 0.2% by mass to 5% by mass of a surface treatment agent, more preferably 0.3% by mass by 0.3% by mass. It is more preferable that the surface is treated in an amount of 2 to 2% by mass.

The degree of surface treatment by a surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of the inorganic filler is 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 viewpoint of preventing an increase in the melt viscosity of the resin composition or the melt viscosity in sheet form, 1.0 mg/m2 or less is preferable, 0.8 mg/m2 or less is more preferable, and 0.5 mg/m2 or less is still more preferable. .

(C) The amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with a surface treatment agent, and ultrasonic 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 a carbon analyzer, "EMIA-320V" manufactured by Horiba Sesakusho, etc. can be used.

(C) The content of the inorganic filler is preferably 30% by mass or more, more preferably 60% by mass or more, assuming that the non-volatile component in the resin composition is 100% by mass, from the viewpoint of obtaining a cured product with a low dielectric loss tangent. , more preferably 65 mass% or more, preferably 85 mass% or less, more preferably 80 mass% or less, and even more preferably 75 mass% or less.

<(D) Radical polymerizable resin>

The resin composition may be combined with the above-mentioned components (A) to (C) and may further contain (D) radically polymerizable resin as an optional component. The (D) radically polymerizable resin as this (D) component does not include the components corresponding to the above-mentioned (A) to (C) components.

The type of radically polymerizable resin is not particularly limited as long as it has one or more (preferably two or more) radically polymerizable unsaturated groups per molecule. Examples of the radically polymerizable resin include radically polymerizable unsaturated groups such as maleimide group, vinyl group, allyl group, styryl group, vinylphenyl group, acryloyl group, methacryloyl group, propenyl group, fumaroyl group, and Resins having one or more types selected from maleyl groups can be mentioned. Among these, from the viewpoint of significantly obtaining the effects of the present invention, the radical polymerizable resin is preferably at least one selected from maleimide resin, (meth)acrylic resin, and Schiryl resin, and maleimide resin is more preferable.

As a maleimide resin, as long as it has one or more (preferably two or more) maleimide groups (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl group) per molecule, The type is not particularly limited. As maleimide resin, for example, (1) “BMI-3000J”, “BMI-5000”, “BMI-1400”, “BMI-1500”, “BMI-1700”, “BMI-689” (all designer Maleimide resins containing an aliphatic skeleton (preferably an aliphatic skeleton with 36 carbon atoms derived from dimerdiamine), such as "SLK6895-T90" (manufactured by Molecules Co., Ltd.) and "SLK6895-T90" (manufactured by Shinetsu Chemical Co., Ltd.); (2) a maleimide resin containing an indan skeleton, described in the Invention Association Public Notice No. 2020-500211; (3) Nitrogen atom of maleimide group, such as "MIR-3000-70MT" (manufactured by Nippon Kayaku Co., Ltd.), "BMI-4000" (manufactured by Yamato Kasei Co., Ltd.), and "BMI-80" (manufactured by KAI Kasei Co., Ltd.) and a maleimide resin containing an aromatic ring skeleton directly bonded to it.

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

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

The content of component (D) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, assuming that the non-volatile component in the resin composition is 100% by mass, from the viewpoint of significantly obtaining the effect of the present invention. More preferably, it is 0.5 mass% or more, preferably 5 mass% or less, more preferably 3 mass% or less, and even more preferably 2 mass% or less.

<(E) Curing accelerator>

The resin composition may further contain (E) a curing accelerator as an optional component in combination with the components (A) to (C) described above. The (E) hardening accelerator as this (E) component does not include those corresponding to the above-mentioned (A) to (D) components. (E) The curing accelerator has a function as a curing catalyst that promotes curing of the epoxy resin in the (B) thermosetting resin.

(E) As a curing accelerator, a compound that promotes curing of the epoxy resin can be used. Examples of such (E) curing accelerator include phosphorus-based curing accelerator, urea-based curing accelerator, guanidine-based curing accelerator, imidazole-based curing accelerator, metal-based curing accelerator, and amine-based curing accelerator. (E) The curing accelerator may be used individually or in combination of two or more types.

Examples of phosphorus-based curing accelerators include tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, and bis(tetrabutylphosphonium)pyrro. Mellitate, tetrabutylphosphonium hydrogenhexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, di-tert-butyldimethylphosphonium Aliphatic phosphonium salts such as tetraphenyl borate; Methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra- p-tolyl borate, tetraphenylphosphonium tetraphenyl borate, tetraphenylphosphonium tetrap-tolyl borate, triphenylethylphosphonium tetraphenyl borate, tris (3-methylphenyl) ethylphosphonium tetraphenyl borate, tris (2-methyl aromatic phosphonium salts such as toxyphenyl)ethylphosphonium tetraphenyl borate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate; Aromatic phosphine/borane complexes such as triphenylphosphine/triphenylborane; Aromatic phosphine/quinone addition reactants such as triphenylphosphine/p-benzoquinone addition reactants; Tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl(2-butenyl)phosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, Aliphatic phosphines such as tricyclohexylphosphine; Dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolyl Phosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-isopropylphenyl)phosphine, Tris(4-butylphenyl)phosphine, tris(4-tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,5-dimethylphenyl)phosphine, tris(2, 6-dimethylphenyl)phosphine, tris(3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine , tris(2-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl- 2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2- and aromatic phosphines such as bis(diphenylphosphino)acetylene and 2,2'-bis(diphenylphosphino)diphenyl ether.

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

Examples of guanidine-based curing accelerators include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, and diphenylguanidine. , trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]deca-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0] Deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1, Examples include 1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, and 1-(o-tolyl) biguanide.

Examples of imidazole-based curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methyl. Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Imidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2- Ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimida Zolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-unde Cylimidazolyl-(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-phenylimidazolisocyanuric acid Adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1, 2-a] Imidazole compounds such as benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, and imidazole compounds and epoxy resins Adduct forms of . Commercially available imidazole-based curing accelerators include, for example, "1B2PZ", "2E4MZ", "2MZA-PW", "2MZ-OK", "2MA-OK", and "2MA-OK-" manufactured by Shikoku Kaseikogyo Co., Ltd. PW”, “2PHZ”, “2PHZ-PW”, “Cl1Z”, “Cl1Z-CN”, “Cl1Z-CNS”, “C11Z-A”; and “P200-H50” manufactured by Mitsubishi Chemical Corporation.

Examples of the metal-based curing accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Examples include organic zinc complexes, organic iron complexes such as iron(III) acetylacetonate, organic nickel complexes such as nickel(II) acetylacetonate, and organic manganese complexes such as manganese(II) acetylacetonate. Examples of organometallic salts include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

Examples of amine-based curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6,-tris(dimethylaminomethyl)phenol, 1, Examples include 8-diazabicyclo(5,4,0)-undecene. As an amine-type hardening accelerator, a commercial item may be used, for example, "MY-25" manufactured by Ajinomoto Fine Techno Co., Ltd., etc.

(E) The content of the curing accelerator is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, assuming that the non-volatile component in the resin composition is 100% by mass, from the viewpoint of significantly obtaining the effect of the present invention. More preferably, it is 0.03 mass% or more, preferably 1 mass% or less, more preferably 0.5 mass% or less, and even more preferably 0.1 mass% or less.

<(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-mentioned (A) to (E) components. As the organic filler, any organic filler that can be used when forming the insulating layer of a printed wiring board may be used, and examples include rubber particles, polyamide fine particles, silicon particles, etc.

As the rubber particles, commercially available products may be used, and examples include "EXL2655" manufactured by Dow Chemical Nippon Corporation, "AC3401N" and "AC3816N" manufactured by Aika Kogyo Corporation.

(F) The content of the organic filler is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, assuming that the non-volatile component in the resin composition is 100% by mass, from the viewpoint of significantly obtaining the effect of the present invention. More preferably, it is 0.5 mass% or more, preferably 3 mass% or less, more preferably 2 mass% or less, and even more preferably 1.5 mass% or less.

<(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 component (G) does not include those corresponding to the components (A) to (F) described above.

(G) Thermoplastic resins include, for example, polyimide resin, phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyamidoimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, Polyphenylene ether resin, polycarbonate resin, polyether ether ketone resin, polyester resin, etc. can be mentioned. (G) In one embodiment, the thermoplastic resin preferably contains a thermoplastic resin selected from the group consisting of polyimide resin and phenoxy resin, and more preferably contains phenoxy resin. In addition, thermoplastic resins may be used individually, or may be used in combination of two or more types.

Specific examples of the polyimide resin include “SLK-6100” manufactured by Shin-Etsu Chemical Co., Ltd., “Licca Coat SN20” and “Licca Coat PN20” manufactured by Nippon Rika Co., Ltd.

Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, and naphthalene. and a phenoxy resin having at least one type of skeleton selected from the group consisting of 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.

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 (phenoxy resin containing bisphenol S skeleton); “YX6954” manufactured by Mitsubishi Chemical Corporation (phenoxy resin containing bisphenol acetophenone skeleton); “FX280” and “FX293” manufactured by Nittetsu Chemical & Materials, Inc.; "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7482" and "YL789" manufactured by Mitsubishi Chemical Corporation 1BH30” and the like.

Examples of the polyvinyl acetal resin include polyvinyl formal resin and polyvinyl butyral resin, with polyvinyl butyral resin being preferred. Specific examples of the polyvinyl acetal resin include “Denka Butyral 4000-2”, “Denka Butyral 5000-A”, “Denka Butyral 6000-C”, and “Denka Butyral 6000-EP” manufactured by Denka Corporation; S-Lec BH series, BX series (e.g. BX-5Z), KS series (e.g. KS-1), BL series, BM series manufactured by Sekisui Kagakukogyo Co., Ltd.; etc. can be mentioned.

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-based polymers such as polypropylene and ethylene-propylene block copolymer.

Examples of the polybutadiene resin include hydrogenated polybutadiene skeleton-containing resin, hydroxyl group-containing polybutadiene resin, phenolic hydroxyl group-containing polybutadiene resin, carboxyl group-containing polybutadiene resin, acid anhydride group-containing polybutadiene resin, and epoxy group-containing poly. Examples include butadiene resin, isocyanate group-containing polybutadiene resin, urethane group-containing polybutadiene resin, and polyphenylene ether-polybutadiene resin.

Specific examples of polyamide-imide resin include “Viromax HR11NN” and “Viromax HR16NN” manufactured by Toyobo Co., Ltd. Specific examples of polyamideimide resins include modified polyamideimides such as "KS9100" and "KS9300" (polyamideimide containing a polysiloxane skeleton) manufactured by Hitachi Kasei Corporation.

Specific examples of the polyether sulfone resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd.

Specific examples of polysulfone resins include polysulfone “P1700” and “P3500” manufactured by Solvay Advanced Polymers.

Specific examples of polyphenylene ether resin include "NORYL SA90" manufactured by SABIC. Specific examples of polyetherimide resin include “Ultem” manufactured by GE Corporation.

Examples of polycarbonate resins include carbonate resins containing hydroxy groups, carbonate resins containing phenolic hydroxyl groups, carbonate resins containing carboxyl groups, carbonate resins containing acid anhydride groups, carbonate resins containing isocyanate groups, carbonate resins containing urethane groups, and the like. Specific examples of polycarbonate resin include “FPC0220” manufactured by Mitsubishi Gas Chemicals, “T6002” and “T6001” (polycarbonate diol) manufactured by Asahi Kasei Chemicals, and “C-1090” and “C-2090” manufactured by Kuraray Corporation. ", "C-3090" (polycarbonate diol), etc. Specific examples of polyetheretherketone resin include "Sumipro K" manufactured by Sumitomo Chemical Co., Ltd.

Examples of polyester resin include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polytrimethylene terephthalate resin, polytrimethylene naphthalate resin, and polycyclohexane dimethyl terephthalate. Phthalate resin, etc. can be mentioned.

(G) The weight average molecular weight (Mw) of the thermoplastic resin is preferably 5,000 or more, more preferably 8,000 or more, further preferably 10,000 or more, especially preferably 20,000 or more from the viewpoint of significantly obtaining the effects of the present invention. , preferably 100,000 or less, more preferably 70,000 or less, even more preferably 60,000 or less, especially preferably 50,000 or less.

(G) The content of the thermoplastic resin is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, assuming that the non-volatile component in the resin composition is 100% by mass, from the viewpoint of significantly obtaining the desired effect of the present invention. , more preferably 0.3 mass% or more, preferably 5 mass% or less, more preferably 4 mass% or less, even more preferably 3 mass% or less.

<(H) Other additives>

In addition to the components mentioned above, 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, antifoaming agents, leveling agents, adhesion imparting agents, flame retardants, etc. These may be used individually, or two or more types may be used in combination at any ratio.

The resin composition can be manufactured, for example, by mixing the above-mentioned components in any order. Additionally, in the process of mixing each component, heating and/or cooling may be performed by appropriately adjusting the temperature. Additionally, during or after mixing each component, stirring may be performed using a stirring device such as a mixer to uniformly disperse each component. Additionally, if necessary, the resin composition may be subjected to defoaming treatment.

<Physical properties and uses of resin composition>

Since the resin composition contains component (A), it becomes possible to obtain a cured product with a high glass transition temperature (Tg). In addition, the resin composition generally makes it possible to obtain a cured product with high peel strength and low dielectric loss tangent.

The cured product obtained by curing the resin composition at 190°C for 90 minutes exhibits the characteristic of high glass transition temperature (Tg). Therefore, an insulating layer with a high glass transition temperature is formed. 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, but can be, for example, 300°C or lower. The glass transition temperature (Tg) can be measured by the method described in the Examples described later.

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 high peeling strength between plating and plating. Therefore, when an insulating layer is formed from this cured material, an insulating layer with a high peeling strength between the cured material and the conductor layer can be obtained. The peeling 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 even 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. Peel strength can be measured by the method described in the Examples described later.

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

The resin composition of the present invention is suitable as a resin composition for insulation purposes, and is 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). In addition, the resin composition is suitable as a resin composition for forming the insulating layer (resin composition for forming an insulating layer for forming a conductor layer) for forming a conductor layer (including a rewiring layer) formed on the insulating layer. do. The resin composition also includes sheet-like laminate materials such as resin sheets and prepregs, solder resists, underfill materials, die bonding materials, semiconductor sealants, hole filling resins, component filling resins, multi-chip packages, package-on-packages, wafer-level packages, It can be used in a wide range of applications where the resin composition can be used, such as panel level packaging and system-in-package.

In addition, for example, when a semiconductor chip package is manufactured through the following processes (1) to (6), the resin composition according to this embodiment is used to form a redistribution forming layer as an insulating layer for forming a redistribution layer. It is also suitable as a resin composition for sealing a semiconductor chip (a resin composition for forming a redistribution layer) and a resin composition for sealing a semiconductor chip (a resin composition for sealing a semiconductor chip). When a semiconductor chip package is manufactured, a rewiring layer may be additionally formed on the sealing layer.

(1) A process of laminating a temporarily fixed film on a substrate,

(2) A process of temporarily fixing a semiconductor chip on a temporarily fixing film,

(3) Process of forming a sealing layer on the semiconductor chip,

(4) A process of peeling the base material and temporarily fixed film from the semiconductor chip,

(5) A process of forming a redistribution layer as an insulating layer on the surface of the semiconductor chip from which the substrate and temporarily fixed film are peeled, and

(6) Process of forming a redistribution layer as a conductor layer on the redistribution formation layer

The above-mentioned resin composition can be used even when the printed wiring board is a circuit board with built-in components.

[Resin sheet]

The resin sheet of the present invention includes a support and a resin composition layer formed from the resin composition of the present invention provided on the support.

The thickness of the resin composition layer is preferably 100 μm or less, more preferably 75 μm or less, from the viewpoint of reducing the thickness of the printed wiring board and providing a cured product with excellent insulation even if the cured product of the resin composition is a thin film. More preferably, it is 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.

Examples of the support include films made of plastic materials, metal foils, and release papers, and films and metal foils made of plastic materials are preferred.

When using a film made of a plastic material as a support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyethylene naphthalate (hereinafter sometimes abbreviated as “PEN”) .), polyester, polycarbonate (hereinafter sometimes abbreviated as “PC”), acrylic, polymethyl methacrylate (PMMA), cyclic polyolefin, triacetylcellulose (TAC), and polyether sulfide (PES). ), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is especially preferable.

When using a metal foil as a support, examples of the metal foil include copper foil, aluminum foil, etc., and copper foil is preferable. As the copper foil, a foil made of the simple metal of copper may be used, or a foil made of an alloy of copper and other metals (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. good night.

The support may be subjected to mat treatment, corona treatment, or antistatic treatment on the surface joined to the resin composition layer.

Additionally, as the support, you may use a support with a mold release layer that has a mold release layer on the surface bonded to the resin composition layer. Examples of the release agent used in the release layer of the support with a release layer include at least one type of release agent selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. The support with the release layer may be a commercially available product, for example, "SK-1", "AL-5", and "AL-" manufactured by Lintec, which are PET films with a release layer containing an alkyd resin-based release agent as a main component. 7”, “Lumira T60” manufactured by Torres, “Purex” manufactured by Teijin, and “Unifill” manufactured by Unichika.

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. On the other hand, when using a support body with a release layer, it is preferable that the entire thickness of the support body with a release layer is within the above range.

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 side of the resin composition layer that is not bonded to the support (that is, the side opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating a protective film, adhesion of dust or the like to the surface of the resin composition layer and scratches can be suppressed.

The resin sheet can be manufactured, for example, by preparing a resin varnish in which a resin composition is dissolved in an organic solvent, applying this resin varnish on a support using a die coater, etc., and further drying to form a resin composition layer. .

Examples of organic solvents include ketones such as acetone, methyl ethyl ketone (MEK), and cyclohexanone; Acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols such as cellosolve and butylcarbitol; aromatic hydrocarbons such as toluene and xylene; and amide-based solvents such as dimethylformamide, dimethylacetamide (DMAc), and N-methylpyrrolidone. Organic solvents may be used individually, or two or more types may be used in combination.

Drying may be performed by known methods such as heating or hot air spraying. Drying conditions are not particularly limited, but the resin composition layer is dried so that the content of the organic solvent is 10% by mass or less, preferably 5% by mass or less. Although it also 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 an organic solvent, the resin composition layer is dried at 50°C to 150°C for 3 to 10 minutes. can be formed.

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

[Printed wiring board]

A printed wiring board according to one embodiment of the present invention includes an insulating layer formed of a cured material obtained by curing the above-described resin composition.

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

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

(II) Process of curing the resin composition layer to form an insulating layer

The “inner layer substrate” used in step (I) is a member that becomes the substrate of the printed wiring board, for example, glass epoxy substrate, metal substrate, polyester substrate, polyimide substrate, BT resin substrate, and thermosetting polyphenylene. Ether substrates, etc. can be mentioned. Additionally, the substrate may have a conductor layer on one or both sides, and this conductor layer may be pattern-processed. An inner layer substrate in which a conductor layer is formed on one or both sides of the substrate is sometimes referred to as an “inner layer circuit board.” Additionally, when manufacturing a printed wiring board, an intermediate product on which an insulating layer and/or a conductor layer must be additionally formed is also included in the “inner layer substrate.” If the printed wiring board is a circuit board with embedded components, an inner layer board with embedded components may be used.

Lamination of the inner layer substrate and the resin sheet can be performed, for example, by heat-pressing the resin sheet to the inner layer substrate from the support side. As a member for heat-pressing the resin sheet to the inner layer substrate (hereinafter also referred to as “heat-pressing member”), for example, a heated metal plate (SUS head plate, etc.) or a metal roll (SUS roll, etc.) can be used. On the other hand, it is preferable not to press the heat-compression member directly on the resin sheet, but to press it through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the inner layer substrate.

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

Lamination can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressurization laminator manufactured by Meiki Sesakusho, a vacuum applicator manufactured by Nikko Materials, and a batch vacuum pressurization laminator.

After lamination, the laminated resin sheets may be smoothed by, for example, pressing a heat-pressing member from the support side under atmospheric pressure. The press conditions for the smoothing treatment can be the same as the heat-pressing conditions for the above-described lamination. Smoothing treatment can be performed using a commercially available laminator. On the other hand, the lamination and smoothing treatment may be performed continuously using the commercially available vacuum laminator.

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

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 of active energy rays such as ultraviolet rays, but is usually thermally cured by heating.

For example, the heat curing conditions of the resin composition layer vary depending on the type of the resin composition, but in one embodiment, the curing temperature is preferably 120l°C to 240°C, more preferably 150°C to 220°C, even more preferably is 170°C to 210°C. The curing time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and even more preferably 15 minutes to 100 minutes.

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 heat curing the resin composition layer, the resin composition layer is cured 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. Preheating may be performed preferably for 5 minutes to 150 minutes, more preferably for 15 minutes to 120 minutes, and even more preferably for 15 minutes to 100 minutes.

The method of manufacturing a printed wiring board may further include (III) a step of perforating the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer. When the support is removed after step (II), the support may be removed between steps (II) and (III), between steps (III) and (IV), or between steps (IV) and (V). It may be carried out in . Additionally, 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.

Process (III) is a process of drilling holes in the insulating layer, thereby forming holes such as via holes and through holes in the insulating layer. Step (III) may be performed using, for example, a drill, laser, or plasma, depending on the composition of the resin composition used to form the insulating layer. The size and shape of the hole may be appropriately determined depending on the design of the printed wiring board.

Process (IV) is a process of roughening the insulating layer. Usually, in this step (IV), removal of smear is also performed. The procedures and conditions of the roughening process are not particularly limited. For example, the insulating layer can be roughened by performing swelling treatment with a swelling liquid, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing liquid in this order.

Examples of the swelling liquid used in the roughening treatment include an alkaline solution and a surfactant solution, and an alkaline solution is preferred. As the alkaline solution, a sodium hydroxide solution or a potassium hydroxide solution is more preferable. Examples of commercially available swelling liquids include “Swelling Deep Securiganth P” and “Swelling Deep Securiganth SBU” manufactured by Atotech Japan. The swelling treatment using the swelling liquid is not particularly limited, but can be performed, 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 swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid of 40°C to 80°C for 5 to 15 minutes.

Examples of the oxidizing agent used in the roughening treatment include an alkaline permanganate solution obtained 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 permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60°C to 100°C for 10 to 30 minutes. Additionally, the concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as “Concentrate Compact CP” and “Dosing Solution Securiganth P” manufactured by Atotech Japan.

As a neutralizing liquid used in the roughening treatment, an acidic aqueous solution is preferable, and examples of commercially available products include "Reduction Solution Securigant P" manufactured by Atotech Japan. Treatment with a neutralizing liquid can be performed by immersing the treated surface that has been roughened with an oxidizing agent in a neutralizing liquid at 30°C to 80°C for 5 to 30 minutes. In terms of workability, etc., a method of immersing the object that has been roughened with an oxidizing agent in a neutralizing liquid at 40°C to 70°C for 5 to 20 minutes is preferable.

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

Step (V) is a step of forming a conductor layer, and the conductor layer is formed on the insulating layer. The conductor material used in the conductor layer is not particularly limited. In a suitable embodiment, the conductor layer comprises one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. do. The conductor layer may be a single metal layer or an alloy layer, and the alloy layer may be, for example, an alloy of two or more metals selected from the above group (e.g., nickel/chromium alloy, copper/nickel alloy, and copper/titanium alloy) ) can include a layer formed of. Among them, from the viewpoint of versatility of 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 a nickel-chromium alloy or copper-nickel alloy , an alloy layer of a copper-titanium alloy is preferred, and a mono-metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of a nickel-chromium alloy is more preferable, and a mono-metal layer of copper This is more preferable.

The conductor layer may have a single-layer structure or a multi-layer structure in which two or more single metal layers or alloy layers made of different 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.

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

The conductor layer is preferably formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating the surface of the insulating layer using a semi-additive method, a full additive method, or the like. From the viewpoint of ease of manufacture, it is preferable to form by the semi-additive method. Below, an example of forming a conductor layer by the semi-additive method will be shown.

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

[Semiconductor device]

A 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.

Semiconductor devices include various semiconductor devices used in electrical appliances (e.g., computers, mobile phones, digital cameras, televisions, etc.) and vehicles (e.g., motorcycles, automobiles, trams, ships, aircraft, etc.). there is.

Example

Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited to the following examples. In the following description, “part” and “%” indicating quantity mean “part by mass” and “% by mass”, respectively, unless otherwise specified. In addition, the operations described below were performed in an environment of normal temperature and pressure unless otherwise specified.

<Example 1A> Synthesis of polyester resin (1)

Dicyclopentadiene-phenol polyadduct (“J-DPP85” manufactured by JFE Chemical, hydroxyl equivalent weight 165 g/eq.) was placed in a 0.3 liter four-necked round flask equipped with a stirring device, thermometer, dropping funnel, and nitrogen gas inlet. 11.4 g, 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, stirred while blowing nitrogen gas, and heated to 30°C to dissolve. . Finally, 16.6 g of a 25% caustic soda aqueous solution was added dropwise, paying attention to heat generation, to raise the temperature to 60°C. The time required for loading was 15 minutes. After stirring at 60°C for another hour, 25 g of distilled water was added and stirred, and the aqueous layer was discarded. Additionally, the organic layer was washed three times using the same operation. The organic layer was dried with sodium sulfate, the dry material was filtered, and a part of the solvent was distilled off from the obtained solution to produce the desired polyester resin (1) containing 45% by mass of toluene (active group equivalent of about 215 g/eq., bio 24.7 g of toluene solution with a mass ratio of 28.4 mass% and a nonvolatile component ratio of 55% was obtained.

The obtained polyester resin (1) was measured by gel permeation chromatography (GPC) and infrared spectroscopy (IR) based on the following GPC measurement conditions and IR measurement conditions. The GPC chart of polyester resin (1) is shown in Figure 1, and the IR chart is shown in Figure 2. In the mass spectrum (ESI) of polyester resin (1), m/z = 407 (MH) ^- corresponding to n = 0 in the theoretical structure of the target material, m / z = 847 (MH) corresponding to n = 1 ) ^- , 849(M+H) ⁺ each spectrum was observed. Additionally, the number average molecular weight of polyester resin (1) by GPC was 1572. As a result, it was confirmed that the obtained polyester resin (1) had the following molecular structure (where n is 0≤n≤8 and a represents a number in the range of 0 to 4).

(GPC measurement conditions)

Measuring device: “HLC-8420GPC” manufactured by Tosoh Corporation.

Column: Guard column “HXL-L” manufactured by Tosoh + “TSK-GEL Super HZ2000” manufactured by Tosoh + “TSK-GEL Super HZ2000” manufactured by Tosoh + “TSK-GEL Super HZ3000” manufactured by Tosoh + “TSK-GEL Super HZ2000” manufactured by Tosoh. TSK-GEL Super HZ4000」

Detector: RI (differential refractometer)

Data processing: “GPC workstation EcoSEC-WorkStation” manufactured by Tosoh Corporation

Column temperature: 40℃

Development Solvent: Tetrahydrofuran

Flow rate: 0.35mL/min

Standard: Based on the measurement manual of the above-mentioned “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: 0.2 mass% tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (10 μL)

(IR measurement conditions)

Measuring device: PIKE Technologiesshasei 「GladiATR」

<Example 2A> Synthesis of polyester resin (2)

Dicyclopentadiene-phenol polyadduct (“J-DPP85” manufactured by JFE Chemical, hydroxyl equivalent weight 165 g/eq.) was placed in a 0.3 liter four-necked round flask equipped with a stirring device, thermometer, dropping funnel, and nitrogen gas inlet. 10 g, 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, stirred while blowing nitrogen gas, and heated to 30°C to dissolve. Finally, 14.6 g of 25% caustic soda aqueous solution was added dropwise, paying attention to heat generation, to raise the temperature to 60°C. The time required for dropping was 10 minutes. After stirring at 60°C for 1 hour, 25 g of distilled water was added and stirred, and the aqueous layer was discarded. Additionally, the organic layer was washed three times using the same operation. The organic layer was dried with sodium sulfate, the dry material was filtered, and a portion of the solvent was distilled off from the resulting solution to produce the desired polyester resin (2) containing 50% by mass of toluene (active group equivalent of about 223 g/eq., bio 27.6 g of toluene solution with a mass ratio of 0 mass% and a nonvolatile component ratio of 50% was obtained.

The obtained polyester resin (2) was measured by gel permeation chromatography (GPC) and infrared spectroscopy (IR) under the same conditions as for polyester resin (1). The GPC chart of polyester resin (2) is shown in FIG. 3, and the IR chart is shown in FIG. 4. Additionally, the number average molecular weight of polyester resin (2) by GPC was 2152. In mass spectrum (ESI), in the theoretical structure of the target substance, m/z=425(M+H) ⁺ corresponding to n=0, and m/z=882(M+H) ⁺ corresponding to n=1. Each spectrum was observed. As a result, it was confirmed that the obtained polyester resin (2) had 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)

In the esterification of Example 1A, 4.98 g of 1-naphthol was replaced with 3.26 g of phenol. In the same manner as in Example 1A except for the above, polyester resin (3) having the following molecular structure (number average molecular weight 1447, active group equivalent weight approximately 198 g/eq., biomass ratio 30.8% by mass, nonvolatile component ratio 55%) toluene solution) was obtained (where n is 0≤n≤8 and a represents a number in the range of 0 to 4).

<Example 4A> Synthesis of polyester resin (4)

In the esterification of Example 1A, 4.98 g of 1-naphthol was replaced with 5.89 g of orthophenylphenol. Except the above, in the same manner as in Example 1A, polyester resin (4) having the following molecular structure (number average molecular weight 1889, active group equivalent weight approximately 224 g/eq., biomass ratio 27.3 mass%, nonvolatile component ratio 55 % toluene solution) was obtained (where n is 0≤n≤8 and a represents a number ranging from 0 to 4).

<Example 5A> Synthesis of polyester resin (5)

In the esterification of Example 1A, 11.4 g of dicyclopentadiene-phenol polyadduct (“J-DPP85” manufactured by JFE Chemicals, hydroxyl equivalent weight 165 g/eq.) was mixed with 58.8 g of SA90 (manufactured by SABIC Innovative Plastics). changed to g. In the same manner as in Example 1A except for the above, polyester resin (5) containing 70% by mass of toluene and having the following molecular structure (number average molecular weight of 4652, active group equivalent of about 675 g/eq., biomass ratio of 9.0 mass) %, a toluene solution with a non-volatile component ratio of 30%) was obtained (where n is 0≤n≤8, and b and c represent numbers in the range of 0 to 4).

<Example 6A> Synthesis of polyester resin (6)

In the esterification of Example 1A, 11.4 g of dicyclopentadiene-phenol polyadduct (“J-DPP85” manufactured by JFE Chemical, hydroxyl equivalent weight 165 g/eq.) was added to 3-(4-hydroxyphenyl)-1. ,1,3-trimethyl-2,3-dihydro-1H-inden-5-ol was replaced with 9.28g. In the same manner as in Example 1A except for the above, polyester resin (6) having the following molecular structure (number average molecular weight 1297, active group equivalent weight approximately 198 g/eq., biomass ratio 30.9% by mass, nonvolatile component ratio 55%) toluene solution) was obtained (where n is 0≤n≤8).

<Example 7A> Synthesis of polyester resin (7)

In the esterification of Example 1A, 11.4 g of dicyclopentadiene-phenol polyadduct (“J-DPP85” manufactured by JFE Chemical, hydroxyl equivalent weight 165 g/eq.) was reacted with 4,4'-(9-fluorenylic acid). Den)diphenol was changed to 12.1g. In the same manner as in Example 1A except for the above, polyester resin (7) having the following molecular structure (number average molecular weight 1585, active group equivalent weight approximately 225 g/eq., biomass ratio 27.1% by mass, nonvolatile component ratio 55%) toluene solution) was obtained (where n is 0≤n≤8).

<Example 8A> Synthesis of polyester resin (8)

In the esterification of Example 1A, 11.4 g of dicyclopentadiene-phenol polyadduct (“J-DPP85” manufactured by JFE Chemical, hydroxyl equivalent weight 165 g/eq.) was added to 4,4'-dihydroxydiphenyl ether. Changed to 7.00g. In the same manner as in Example 1A except for the above, 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, nonvolatile component ratio 55%) toluene solution) was obtained (where n is 0≤n≤8).

<Example 9A> Synthesis of polyester resin (9)

In the esterification of Example 1A, 11.4 g of dicyclopentadiene-phenol polyadduct (“J-DPP85” manufactured by JFE Chemical, hydroxyl equivalent weight 165 g/eq.) was mixed with 4,4'-dihydroxybenzophenone 7.41. changed to g. In the same manner as in Example 1A except for the above, 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, nonvolatile component ratio 55%) toluene solution) was obtained (where n is 0≤n≤8).

<Example 10A> Synthesis of polyester resin (10)

In the esterification of Example 1A, 11.4 g of dicyclopentadiene-phenol polyadduct (“J-DPP85” manufactured by JFE Chemical, hydroxyl equivalent weight 165 g/eq.) was replaced with 7.90 g of bisphenol A. In the same manner as in Example 1A except for the above, 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, nonvolatile component ratio 55%) toluene solution) was obtained (where n is 0≤n≤8).

<Example 11A> Synthesis of polyester resin (11)

In the esterification of Example 1A, 11.4 g of dicyclopentadiene-phenol polyadduct (“J-DPP85” manufactured by JFE Chemical, hydroxyl equivalent weight 165 g/eq.) was replaced with 6.93 g of bisphenol F. Except the above, in the same manner as in Example 1A, polyester resin (11) having the following molecular structure (number average molecular weight 1168, active group equivalent weight about 175 g/eq., biomass ratio 34.9% by mass, nonvolatile component ratio 55%) toluene solution) was obtained (where n is 0≤n≤8).

<Example 12A> Synthesis of polyester resin (12)

In the esterification of Example 1A, 11.4 g of dicyclopentadiene-phenol polyadduct (“J-DPP85” manufactured by JFE Chemical, hydroxyl equivalent weight 165 g/eq.) was mixed with 10.7 g of 2,2'-diallylbisphenol A. changed to In the same manner as in Example 1A except for the above, polyester resin (12) having the following molecular structure (number average molecular weight of 1468, active group equivalent of about 211 g/eq., biomass ratio of 28.9 mass%, nonvolatile component ratio of 55%) toluene solution) was obtained (where n is 0≤n≤8).

<Example 13A> Synthesis of polyester resin (13)

In the esterification of Example 1A, 11.4 g of dicyclopentadiene-phenol polyadduct (“J-DPP85” manufactured by JFE Chemical, hydroxyl equivalent weight 165 g/eq.) was replaced with 8.66 g of bisphenol S. In the same manner as Example 1A except for the above, 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, nonvolatile component ratio 55%) toluene solution) was obtained (where n is 0≤n≤8).

<Example 14A> Synthesis of polyester resin (14)

In the esterification of Example 1A, 11.4 g of dicyclopentadiene-phenol polyadduct (“J-DPP85” manufactured by JFE Chemical, hydroxyl equivalent weight 165 g/eq.) was reacted with 4,4'-dihydroxybiphenyl 6.44. changed to g. Except for the above, in the same manner as in Example 1A, 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, nonvolatile component ratio 55%) toluene solution) was obtained (where n is 0≤n≤8).

<Example 15A> Synthesis of polyester resin (15)

In the esterification of Example 1A, 11.4 g of dicyclopentadiene-phenol polyadduct (“J-DPP85” manufactured by JFE Chemical, hydroxyl equivalent weight 165 g/eq.) was replaced with 5.54 g of 2,7-naphthalenediol. . In the same manner as in Example 1A except for the above, polyester resin (15) having the following molecular structure (number average molecular weight of 1128, active group equivalent of about 161 g/eq., biomass ratio of 37.8 mass%, non-volatile component ratio of 55%) toluene solution) was obtained (where n is 0≤n≤8).

<Example 16A> Synthesis of polyester resin (16)

In a 0.3 liter four-necked round flask equipped with a stirring device, thermometer, dropping funnel, and nitrogen inlet, 20.0 g of bisphenol A (hydroxyl equivalent 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, stirred while blowing nitrogen gas, and heated to 30°C to dissolve them. Finally, 48 g of a 25% caustic soda aqueous solution was added dropwise, paying attention to heat generation, to raise the temperature to 60°C. The time required for loading was 15 minutes. After stirring at 60°C for another hour, 25 g of distilled water was added and stirred, and the aqueous layer was discarded. Additionally, the organic layer was washed three times through the same operation. The organic layer was dried with sodium sulfate, the dry material was filtered off, and a portion of the solvent was distilled off from the resulting solution to obtain polyester resin (16) with a solid content concentration of 45% by mass (number average molecular weight: 917, active group equivalent: approximately 153 g/eq). ., toluene solution with a biomass ratio > 99% by mass and a nonvolatile component ratio of 45%) was obtained.

The obtained polyester resin (16) was measured by gel permeation chromatography (GPC) and infrared spectroscopy (IR) under the same conditions as for polyester resin (1). The number average molecular weight of the polyester resin according to GPC was 917. The GPC chart of the polyester resin is shown in Figure 5, and the IR chart is shown in Figure 6. Additionally, in the mass spectrum (ESI), in the theoretical structure of the target substance, m/z=309(M+H) ⁺ corresponding to n=0, m/z=658(M+2H) ⁺ corresponding to n=1. Each spectrum of ⁺ was observed. As a result, it was confirmed that the obtained polyester resin had the following molecular structure. In the formula, n represents a number in the range of 0≤n≤8.

<Example 17A> Synthesis of polyester resin (17)

In Example 1A,

1) 4.98 g of 1-naphthol is replaced with 8.0 g of camphene-modified phenol (“YS Resin CP” manufactured by Yasuhara Chemical, hydroxyl equivalent weight 220 g/eq.),

2) 11.4 g of dicyclopentadiene-phenol polyadduct (“J-DPP85” manufactured by JFE Chemical, hydroxyl equivalent weight 165 g/eq.) was replaced with 7.9 g of bisphenol A (hydroxyl equivalent weight 114 g/eq.).

In the same manner as in Example 1A except for the above, polyester resin (17) having the following molecular structure (number average molecular weight 1348, active group equivalent weight approximately 225 g/eq., biomass ratio 88% by mass, nonvolatile component ratio 55%) toluene solution) was obtained.

The obtained polyester resin (17) was measured by gel permeation chromatography (GPC) and infrared spectroscopy (IR) under the same conditions as for polyester resin (1). The number average molecular weight of the polyester resin according to GPC was 1348. The GPC chart of the polyester resin is shown in Figure 7, and the IR chart is shown in Figure 8. Additionally, in the mass spectrum (ESI), m/z=581(M+H) ⁺ corresponding to n=0, m/z=942(M+Na) ⁺ corresponding to n=1 in the theoretical structure of the target substance. Each spectrum was observed. As a result, it was confirmed that the obtained polyester resin had the following molecular structure. In the formula, n represents a number in the range of 0≤n≤8.

<Example 18A> Synthesis of polyester resin (18)

In Example 1A,

1) Replace 4.98g of 1-naphthol with 3.3g of phenol,

2) 11.4 g of dicyclopentadiene-phenol polyadduct (“J-DPP85” manufactured by JFE Chemical, hydroxyl equivalent weight 165 g/eq.) was added to benzyl-modified bisphenol A (in the formula below, d and e are each 1 to 4) represents the integer of and satisfies 1≤d+e≤4) was changed to 14g.

In the same manner as in Example 1A except for the above, polyester resin (18) having the following molecular structure (number average molecular weight 433, active group equivalent weight about 217 g/eq., biomass ratio 71% by mass (n=1 and d+ e=3), toluene solution with a non-volatile content of 46%) was obtained.

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

<Example 1B> Preparation of resin composition and production of resin sheet

15 parts of bisphenol A type epoxy resin (“828EL” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of approximately 180 g/eq., biomass ratio of 0% by mass), biphenyl type epoxy resin (“NC3000L” manufactured by Nippon Kayaku Corporation, epoxy equivalent of approximately 269 g) /eq., biomass ratio 0 mass%), 20 parts, naphthalene type epoxy resin (“ESN475V” manufactured by Nittetsu Chemical & Materials, epoxy equivalent weight approximately 332 g/eq., biomass ratio 0 mass%), 20 parts were stirred, An epoxy resin dissolution composition was prepared, and a triazine skeleton-containing phenolic curing agent (“LA-3018-50P” manufactured by DIC, active group equivalent of approximately 151 g/eq., biomass ratio of 0% by mass, non-volatile) was prepared. 5 parts of 2-methoxypropanol solution with a component ratio of 50%, polyester resin (1) obtained in Example 1A (active group equivalent of about 215 g/eq., biomass ratio of 28.4 mass%, toluene with a non-volatile component ratio of 55%) 40 parts of solution), 4 parts of amine-based curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution with 0% by mass of biomass and 5% by mass of solids), 4 parts of silane coupling agent (KBM-, manufactured by Shinetsu Chemical Co., Ltd.) 573"), 200 parts of spherical silica (“SO-C2” manufactured by Adomatex, average particle diameter 0.5 μm, biomass ratio 0 mass%), phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical, bio 8 parts (1:1 solution of MEK and cyclohexanone with a mass ratio of 0 mass% and non-volatile content of 30 mass%) were mixed and dispersed uniformly with a high-speed rotating mixer to prepare a resin varnish.

Next, resin varnish was uniformly applied on the release surface of the polyethylene terephthalate film (“AL5” manufactured by Lintec, thickness 38 μm) with release treatment as a support so that the thickness of the resin composition layer was 40 μm, and the thickness was 80 to 80 μm. It was dried at 120°C (average 100°C) for 5 minutes to produce a resin sheet.

<Example 2B> Preparation of resin composition and production of resin sheet

In Example 1B,

1) The amount of polyester resin (1) synthesized in Example 1A (toluene solution with an active group equivalent of about 215 g/eq., a biomass ratio of 28.4 mass%, and a non-volatile component ratio of 55%) was changed from 40 parts to 20 parts,

2) Use by adding 15 parts of an active ester compound (“HPC-8000-65T” manufactured by DIC, an active group equivalent of about 223 g/eq., a toluene solution with a biomass ratio of 0 mass% and a non-volatile component ratio of 65%),

3) Spherical silica (“SO-C2” manufactured by Adomatex, average particle diameter 0.5 μm, biomass ratio 0 mass%) surface-treated with a silane coupling agent (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.) Change the amount from 200 parts to 55 parts,

4) The amount of phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Corporation, a 1:1 solution of MEK and cyclohexanone with a biomass ratio of 0 mass% and a non-volatile matter of 30 mass%) was changed from 8 parts to 12 parts.

A resin varnish and a resin sheet were produced in the same manner as in Example 1B except for the above.

<Example 3B>

In Example 1B,

1) 20 parts of biphenyl-type epoxy resin (“NC3000L” manufactured by Nippon Kayaku, epoxy equivalent of about 269 g/eq., biomass ratio of 0% by mass), 20 parts of bixylenol-type epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical, epoxy equivalent) (approximately 194g/eq., biomass ratio 0 mass%) changed to 20 parts,

2) 40 parts of the polyester resin (1) obtained in Example 1A (toluene solution with an active group equivalent of about 215 g/eq., a biomass ratio of 28.4 mass%, and a non-volatile component ratio of 55%) was used as the polyester resin obtained in Example 2A. (2) (Toluene solution with an active group equivalent of about 223 g/eq., a biomass ratio of 0 mass%, and a nonvolatile component ratio of 50%) was changed to 44 parts.

A resin varnish and a resin sheet were produced in the same manner as in Example 1B except for the above.

<Example 4B>

In Example 1B,

1) 20 parts of biphenyl-type epoxy resin (“NC3000L” manufactured by Nippon Kayaku, epoxy equivalent weight of approximately 269 g/eq., biomass ratio of 0% by mass), and a naphthylene ether-type epoxy resin (“HP-6000” manufactured by DIC, Change the epoxy equivalent weight to approximately 250 g/eq. and the biomass ratio to 0 mass% (20 parts).

2) 40 parts of the polyester resin (1) obtained in Example 1A (toluene solution with an active group equivalent of about 215 g/eq., a biomass ratio of 28.4 mass%, and a non-volatile component ratio of 55%) was used as the polyester resin obtained in Example 3A. (3) (toluene solution with an active group equivalent of about 198 g/eq., a biomass ratio of 30.8 mass%, and a non-volatile component ratio of 55%) was changed to 40 parts.

A resin varnish and a resin sheet were produced in the same manner as in Example 1B except for the above.

<Example 5B>

In Example 1B,

1) 20 parts of naphthalene type epoxy resin (“ESN475V” manufactured by Nittetsu Chemical & Materials, epoxy equivalent weight approximately 332 g/eq., biomass ratio 0% by mass), dicyclopentadiene type epoxy resin (manufactured by DIC, “HP”) -7200HH", epoxy equivalent weight approximately 280g/eq., biomass ratio 0 mass%) changed to 15 parts,

2) 6 parts of epoxidized polybutadiene resin (“PB3600M” manufactured by Daicel, non-volatile matter 80 mass%, epoxy equivalent weight approximately 193 g/eq.) were additionally used,

3) 40 parts of the polyester resin (1) obtained in Example 1A (toluene solution with an active group equivalent of about 215 g/eq., a biomass ratio of 28.4 mass%, and a non-volatile component ratio of 55%) was used as the polyester resin obtained in Example 4A. (4) (toluene solution with an active group equivalent of about 224 g/eq., a biomass ratio of 27.3 mass%, and a nonvolatile component ratio of 55%) was changed to 40 parts.

A resin varnish and a resin sheet were produced in the same manner as in Example 1B except for the above.

<Example 6B>

In Example 1B,

1) Phenol-based curing agent containing a triazine skeleton (“LA-3018-50P” manufactured by DIC, 2-methoxypropanol solution with an active group equivalent of about 151 g/eq., a biomass ratio of 0 mass%, and a non-volatile component ratio of 50%) Replace 5 parts with 3 parts of naphthol-type hardener (“SN-485” manufactured by Nittetsu Chemical & Materials, hydroxyl equivalent weight approximately 205 g/eq., biomass ratio 0 mass%),

2) 40 parts of the polyester resin (1) obtained in Example 1A (toluene solution with an active group equivalent of about 215 g/eq., a biomass ratio of 28.4 mass%, and a non-volatile component ratio of 55%) was used as the polyester resin obtained in Example 5A. (5) (toluene solution with an active group equivalent of about 675 g/eq., a biomass ratio of 9.0 mass%, and a nonvolatile component ratio of 30%) was changed to 72 parts.

A resin varnish and a resin sheet were produced in the same manner as in Example 1B except for the above.

<Example 7B>

In Example 1B,

1) Use 5 parts of a prepolymer of bisphenol A dicyanate (“BA230S75” manufactured by Lonza Japan, a MEK solution with a cyanate equivalent of about 232 g/eq., a biomass ratio of 0% by mass, and a non-volatile content of 75% by mass),

2) 40 parts of the polyester resin (1) obtained in Example 1A (toluene solution with an active group equivalent of about 215 g/eq., a biomass ratio of 28.4 mass%, and a non-volatile component ratio of 55%) was used as the polyester resin obtained in Example 6A. (6) (toluene solution with an active group equivalent of about 198 g/eq., a biomass ratio of 30.9 mass%, and a non-volatile component ratio of 55%), changed to 40 parts,

3) Two parts of a 1% by mass MEK solution of cobalt (III) acetylacetonate ((Co(III), manufactured by Tokyo Kasei Co., Ltd., biomass ratio 0% by mass) were additionally used.

A resin varnish and a resin sheet were produced in the same manner as in Example 1B except for the above.

<Example 8B>

In Example 1B,

1) 40 parts of the polyester resin (1) obtained in Example 1A (toluene solution with an active group equivalent of about 215 g/eq., a biomass ratio of 28.4 mass%, and a non-volatile component ratio of 55%) was used as the polyester resin obtained in Example 7A. (7) (toluene solution with an active group equivalent of about 225 g/eq., a biomass ratio of 27.1 mass%, and a non-volatile component ratio of 55%), changed to 40 parts,

2) 4 parts of amine-based curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution with biomass ratio of 0% by mass and solid content of 5% by mass), 4 parts of imidazole-based curing accelerator (“1B2PZ” manufactured by Shikoku Kaseiko Co., Ltd., 1 part) -benzyl-2-phenylimidazole, MEK solution with a solid content of 10% by mass) was changed to 3 parts.

A resin varnish and a resin sheet were produced in the same manner as in Example 1B except for the above.

<Example 9B>

In Example 1B,

1) 40 parts of the polyester resin (1) obtained in Example 1A (toluene solution with an active group equivalent of about 215 g/eq., a biomass ratio of 28.4 mass%, and a non-volatile component ratio of 55%) was used as the polyester resin obtained in Example 8A. (8) (Toluene solution with an active group equivalent of about 175 g/eq., a biomass ratio of 34.8 mass%, and a non-volatile component ratio of 55%) is changed to 40 parts,

2) 3 parts of rubber particles (“Staphyroid AC3816N” manufactured by Aika Kogyo Co., Ltd., biomass ratio 0% by mass) were additionally used.

A resin varnish and a resin sheet were produced in the same manner as in Example 1B except for the above.

<Example 10B>

In Example 1B,

1) 40 parts of the polyester resin (1) obtained in Example 1A (toluene solution with an active group equivalent of about 215 g/eq., a biomass ratio of 28.4 mass%, and a non-volatile component ratio of 55%) was used as the polyester resin obtained in Example 9A. (9) (Toluene solution with an active group equivalent of about 179 g/eq., a biomass ratio of 34.0 mass%, and a non-volatile component ratio of 55%) is changed to 40 parts,

2) 7 parts of biphenyl aralkyl novolac type maleimide (“MIR-3000-70MT” manufactured by Nippon Kayaku Co., Ltd., MEK/toluene mixed solution with a non-volatile content of 70%) were additionally used.

A resin varnish and a resin sheet were produced in the same manner as in Example 1B except for the above.

<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 215 g/eq., a biomass ratio of 28.4 mass%, and a non-volatile component ratio of 55%) was used as the polyester resin obtained in Example 10A. (10) (Toluene solution with an active group equivalent of about 184 g/eq., a biomass ratio of 33.1 mass%, and a non-volatile component ratio of 55%) is changed to 40 parts,

2) 5 parts of bismaleimide-terminated polyimide compound (“BMI-1500” manufactured by DMI) were additionally used.

A resin varnish and a resin sheet were produced in the same manner as in Example 1B except for the above.

<Example 12B>

In Example 1B,

1) 40 parts of the polyester resin (1) obtained in Example 1A (toluene solution with an active group equivalent of about 215 g/eq., a biomass ratio of 28.4 mass%, and a non-volatile component ratio of 55%) was used as the polyester resin obtained in Example 11A. (11) (toluene solution with an active group equivalent of about 175 g/eq., a biomass ratio of 34.9 mass%, and a non-volatile component ratio of 55%), changed to 40 parts,

2) 8 parts of vinylbenzyl-modified polyphenylene ether (“OPE-2St 2200” manufactured by Mitsubishi Gas Chemical Co., Ltd., toluene solution with a non-volatile content of 65%) was additionally used.

A resin varnish and a resin sheet were produced in the same manner as in Example 1B except for the above.

<Example 13B>

In Example 1B,

1) 40 parts of the polyester resin (1) obtained in Example 1A (toluene solution with an active group equivalent of about 215 g/eq., a biomass ratio of 28.4 mass%, and a non-volatile component ratio of 55%) was used as the polyester resin obtained in Example 12A. (12) (toluene solution with an active group equivalent of about 211 g/eq., a biomass ratio of 28.9 mass%, and a non-volatile component ratio of 55%), changed to 40 parts,

2) Spherical silica surface-treated with a silane coupling agent (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.) (“SO-C2” manufactured by Adomatex, average particle diameter 0.5 ㎛, biomass ratio 0 mass%) 200 part was replaced with 55 parts of spherical silica (“UFP-30” manufactured by Denka, average particle diameter 0.3 μm, biomass ratio 0% by mass) surface-treated with a silane coupling agent (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.) ,

3) The amount of phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Co., Ltd., a 1:1 solution of MEK and cyclohexanone with a biomass ratio of 0 mass% and a non-volatile matter of 30 mass%) was changed from 8 parts to 12 parts.

A resin varnish and a resin sheet were produced in the same manner as in Example 1B except for the above.

<Example 14B>

In Example 1B,

1) 40 parts of the polyester resin (1) obtained in Example 1A (toluene solution with an active group equivalent of about 215 g/eq., a biomass ratio of 28.4 mass%, and a non-volatile component ratio of 55%) was used as the polyester resin obtained in Example 13A. (13) (toluene solution with an active group equivalent of about 192 g/eq., a biomass ratio of 31.9 mass%, and a non-volatile component ratio of 55%), changed to 40 parts,

2) Change the amount of amine-based curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution with a biomass ratio of 0 mass% and a solid content of 5 mass%) from 4 parts to 2 parts,

3) 1.5 parts of an imidazole-based curing accelerator (“1B2PZ” manufactured by Shikoku Kasei Kogyo Co., Ltd., a MEK solution containing 10% by mass of 1-benzyl-2-phenylimidazole solids) was additionally used.

A resin varnish and a resin sheet were produced in the same manner as in Example 1B except for the above.

<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 215 g/eq., a biomass ratio of 28.4 mass%, and a non-volatile component ratio of 55%) was used as the polyester resin obtained in Example 14A. (14) (toluene solution with an active group equivalent of about 170 g/eq., a biomass ratio of 35.9 mass%, and a non-volatile component ratio of 55%) is changed to 40 parts,

2) Additional 8 parts of vinylbenzyl-modified polyphenylene ether (“OPE-2St 2200” manufactured by Mitsubishi Gas Chemical Co., Ltd., toluene solution with a non-volatile content of 65%) were additionally used,

3) 8 parts of phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Corporation, a 1:1 solution of MEK and cyclohexanone with a biomass ratio of 0 mass% and a non-volatile matter of 30 mass%) were not used.

A resin varnish and a resin sheet were produced in the same manner as in Example 1B except for the above.

<Example 16B>

In Example 1B,

1) Change the amount of naphthalene type epoxy resin (“ESN475V” manufactured by Nittetsu Chemical & Materials, epoxy equivalent weight approximately 332 g/eq., biomass ratio 0 mass%) from 20 parts to 15 parts,

2) 6 parts of epoxidized polybutadiene resin (“PB3600M” manufactured by Daicel, non-volatile matter 80 mass%, epoxy equivalent weight approximately 193 g/eq.) were additionally used,

3) 40 parts of the polyester resin (1) obtained in Example 1A (toluene solution with an active group equivalent of about 215 g/eq., a biomass ratio of 28.4 mass%, and a non-volatile component ratio of 55%), as the polyester resin obtained in Example 15A. (15) (toluene solution with an active group equivalent of about 161 g/eq., a biomass ratio of 37.8 mass%, and a non-volatile component ratio of 55%), changed to 40 parts,

4) Spherical silica (“SO-C2” manufactured by Adomatex, average particle diameter 0.5 μm, biomass ratio 0 mass%) surface-treated with a silane coupling agent (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.) Change the amount from 200 to 245,

5) The amount of phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Corporation, a 1:1 solution of MEK and cyclohexanone with a biomass ratio of 0 mass% and a non-volatile matter of 30 mass%) was changed from 8 parts to 5 parts.

A resin varnish and a resin sheet were produced in the same manner as in Example 1B except for the above.

<Example 17B>

In Example 1B,

1) The amount of polyester resin (1) synthesized in Example 1A (toluene solution with an active group equivalent of about 215 g/eq., a biomass ratio of 28.4 mass%, and a non-volatile component ratio of 55%) was changed from 40 parts to 20 parts,

2) 24 parts of polyester resin (16) synthesized in Example 16A (active group equivalent of about 153 g/eq., biomass ratio > 99% by mass, toluene solution with non-volatile component ratio of 45%) was additionally used.

A resin varnish and a resin sheet were produced in the same manner as in Example 1B except for the above.

<Example 18B>

In Example 1B,

1) The amount of polyester resin (1) synthesized in Example 1A (toluene solution with an active group equivalent of about 215 g/eq., a biomass ratio of 28.4 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 (toluene solution with an active group equivalent of about 225 g/eq., a biomass ratio of 88 mass%, and a non-volatile component ratio of 55%) was additionally used.

A resin varnish and a resin sheet were produced in the same manner as in Example 1B except for the above.

<Example 19B>

In Example 1B,

1) The amount of polyester resin (1) synthesized in Example 1A (toluene solution with an active group equivalent of about 215 g/eq., a biomass ratio of 28.4 mass%, and a non-volatile component ratio of 55%) was changed from 40 parts to 20 parts,

2) Polyester resin (18) synthesized in Example 18A (active group equivalent of about 217 g/eq., biomass ratio of 71 mass% (n = 1 and d + e = 3), toluene solution with non-volatile component ratio of 46% ) 24 parts were additionally used.

A resin varnish and a resin sheet were produced in the same manner as in Example 1B except for the above.

<Comparative Example 1>

In Example 1B, 40 parts of the polyester resin (1) obtained in Example 1A (toluene solution with an active group equivalent of about 215 g/eq., a biomass ratio of 28.4 mass%, and a non-volatile component ratio of 55%) was mixed with an active ester compound (DIC). (“HPC-8000-65T” manufactured by the company, toluene solution with an active group equivalent of about 223 g/eq., a biomass ratio of 0 mass%, and a non-volatile component ratio of 65%) was replaced with 35 parts.

A resin varnish and a resin sheet were produced in the same manner as in Example 1B except for the above.

<Measurement of plating peel strength>

(1) Production of base-treated inner layer substrate

A glass cloth-based epoxy resin double-sided copper-clad laminate having copper foil on the surface (copper foil thickness of 18 μm, substrate thickness of 0.8 mm, “R1515A” manufactured by Panasonic Corporation) was prepared. The copper foil on the surface of this inner layer substrate was etched with a copper etching amount of 1 μm using a microetchant (“CZ8101” manufactured by Mack Co., Ltd.), and roughening treatment was performed. After that, drying was performed at 190°C for 30 minutes to produce a base-treated inner layer substrate.

(2) Lamination and curing of resin sheets

The resin sheets obtained in the Examples and Comparative Examples were bonded to the base-treated inner layer substrate using a batch-type vacuum pressure laminator (2-stage build-up laminator "CVP700" manufactured by Nikko Materials) so that the resin composition layer was bonded to the base-treated inner layer substrate. It was laminated on both sides of the substrate. This laminate was performed by reducing the pressure for 30 seconds to bring the atmospheric pressure to 13 hPa or less, and then compressing it at a temperature of 100°C and a pressure of 0.74 MPa for 30 seconds. Next, the laminated resin sheet was smoothed by heat pressing at 100°C and 0.5 MPa under atmospheric pressure for 60 seconds. Furthermore, this was placed in 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 substrate A with a cured resin layer.

(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 Securigant P manufactured by Atotech Japan, a swelling liquid, at 60°C for 10 minutes. Next, it was immersed in Concentrate Compact P (aqueous solution of KMnO ₄ : 60 g/L, NaOH: 40 g/L) manufactured by Atotech Japan, which is a roughening solution, at 80°C for 20 minutes. Finally, it was immersed in the neutralizing solution, Securigant P, a reduction solution manufactured by Atotech Japan, at 40°C for 5 minutes. Subsequently, it was immersed in a solution for electroless plating containing PdCl ₂ at 40°C for 5 minutes, and then immersed in an electroless copper plating solution at 25°C for 20 minutes. After annealing by heating at 150°C for 30 minutes, an etching resist was formed, and after pattern formation by etching, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 30 μm. Next, annealing was performed at 200°C for 60 minutes, and the obtained substrate was referred to as evaluation substrate B.

(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 board B, one end of this was peeled off, pinched with a clamping tool (Autocom type tester “AC-50C-SL” manufactured by TS Corporation), and tested at a speed of 50 mm/min at room temperature. The load (kgf/cm) when 20 mm was removed in the vertical direction was measured based on JIS C6481.

<Measurement of glass transition temperature and dielectric loss tangent of cured product>

(1) Production of hardened product for evaluation

A PET film (“501010” manufactured by Lintech, thickness 50 μm, width 240 mm) having a treated surface on which release treatment was performed and an untreated surface on which release treatment was not performed was prepared. A glass cloth-based epoxy resin double-sided copper-clad laminate (“R5715ES” manufactured by Panasonic, thickness 0.7 mm, width 255 mm) was placed on the untreated side of this PET film, and the four sides were fixed with polyimide adhesive tape (width 10 mm).

Subsequently, the resin varnish prepared in the Examples and Comparative Examples was applied on 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 the temperature was 80°C to 120°C (average 100°C). ) for 10 minutes to obtain a resin sheet. Next, after placing it in an oven at 190°C, the resin composition layer was heat-cured under curing conditions for 90 minutes. After heat curing, the polyimide adhesive tape was peeled off, the glass cloth base epoxy resin double-sided copper clad laminate was peeled off, and the PET film was further peeled to obtain a sheet-like cured product. The obtained cured product is referred to as “cured product for evaluation.”

(2) Measurement of glass transition temperature

The cured product for evaluation was cut to obtain a test piece with a width of about 5 mm and a length of about 15 mm. Thermomechanical analysis was performed on this test piece by the tensile weighting method using a thermomechanical analysis device (“Thermo Plus TMA8310” manufactured by Rigaku Corporation). In detail, after the test piece was mounted on the thermomechanical analysis device, measurements were performed twice in succession under the measurement conditions of a load of 1 g and a temperature increase rate of 5°C/min. And in the second measurement, the glass transition temperature Tg (°C) was calculated.

(3) Measurement of dielectric loss tangent

The cured product for evaluation was cut to 80 mm in length and 2 mm in width to serve as an evaluation sample. For this evaluation sample, the relative dielectric constant 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 made on two test pieces, and the average value was calculated.

<Calculation of biomass ratio>

According to the definition of the Japan Organic Resources Association, “biomass” refers to renewable organic resources derived from living organisms, excluding fossil resources (however, inorganic resources such as shells produced directly by living organisms are included). Based on this definition, the biomass ratio of the raw materials used in the formulation was calculated using the following equation.

Biomass ratio (mass%) = (weight of biologically derived components in the material/weight of the material) × 100

* In the table, the content of component (C) represents the content assuming 100% by mass of the non-volatile component of the resin composition.

Claims (17)

A compound represented by the following formula (A-1).

(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 formulas (A-2) and (A-3),
n represents the number of repetitions and satisfies 0≤n≤8)

(In formula (A-2),
R ¹¹ and R ¹² each independently represent a divalent aromatic group that may have a substituent,
L ¹¹ each independently represents a single bond or a divalent linking group that may have a substituent, and R ¹¹ and L ¹¹ may combine as one to form a ring.
a represents a number ranging from 0 to 5)

(In formula (A-3),
R ¹³ and R ¹⁴ each independently represent a divalent aromatic group that may have a substituent,
L ¹² represents a group represented by formula (A-4).
b and c each independently represent a number ranging from 0 to 5)

(In formula (A-4),
R ¹⁵ and R ¹⁶ each independently represent a divalent aromatic group that may have a substituent,
L ¹³ each independently represents a single bond or a divalent linking group that may have a substituent, and R ¹⁵ and L ¹³ may combine as one to form a ring.
d represents a number ranging from 0 to 5) The compound according to claim 1, wherein R ¹ and R ² in formula (A-1) each independently represent a phenyl group which may have a substituent or a naphthyl group which may have a substituent. In claim 1, R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ in formulas (A-2) and (A-3) each independently have a phenylene group that may have a substituent, or a substituent. A compound representing a naphthylene group that may be present. The compound according to claim 1, wherein R ¹⁵ and R ¹⁶ in formula (A-4) each independently represent a phenylene group which may have a substituent, or a naphthylene group which may have a substituent. In claim 1, L ¹¹ in formula (A-2) is 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 compound representing a sulfonyl group. In claim 1, L ¹¹ in formula (A-2) is each independently a single bond, a divalent aliphatic group which may have a substituent, an oxygen atom, a phenylene group, a fluolenylidene group, a carbonyl group, or a sulfonyl group. A compound representing a group. The compound according to claim 1, wherein X in formula (A-1) represents an oxygen atom. In claim 1, wherein Lee Sang-in, compound. The compound according to claim 1, wherein X in formula (A-1) represents a sulfur atom. The compound according to claim 1, wherein A in formula (A-1) represents one or more groups selected from groups represented by the following formulas (1a) to (4a).

(In the formula, a1 represents a number in the range of 0 to 4, and b1 and c1 each independently represent a number in the range of 0 to 5. “*” represents a bond.) The compound of claim 1, wherein the compound has a number average molecular weight of 5000 or less. In claim 1, the active group equivalent is 100 g/eq. Lee Sang-in, compound. (A) the compound according to any one of claims 1 to 12,
(B) thermosetting resin, and
(C) A resin composition containing an inorganic filler. The resin composition of claim 13, which is used for forming an insulating layer. A resin sheet comprising a support and a resin composition layer provided on the support and containing the resin composition according to claim 13. A printed wiring board comprising an insulating layer formed from a cured product of the resin composition according to claim 13. A semiconductor device comprising the printed wiring board according to claim 16.

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