CN112210045A

CN112210045A - Resin composition

Info

Publication number: CN112210045A
Application number: CN202010656079.9A
Authority: CN
Inventors: 鹤井一彦
Original assignee: Ajinomoto Co Inc
Current assignee: Ajinomoto Co Inc
Priority date: 2019-07-12
Filing date: 2020-07-09
Publication date: 2021-01-12
Also published as: KR20210007874A; JP2021014544A; TW202122492A; JP7200861B2

Abstract

The subject of the invention is to provide: a resin composition which can suppress the curing shrinkage and can give a cured product having an excellent dielectric constant; a resin sheet comprising the resin composition; a printed wiring board, a multilayer flexible substrate and a semiconductor device are provided with an insulating layer formed by using the resin composition. The resin composition comprises (A) a compound having an aromatic ester skeleton and an unsaturated bond and (B) a polyimide resin, wherein the content of the component (B) is 10 to 50 mass% inclusive, based on 100 mass% of nonvolatile components in the resin composition.

Description

Resin composition

Technical Field

The present invention relates to a resin composition. Further, the present invention relates to a resin sheet, a printed wiring board, a multilayer flexible substrate and a semiconductor device obtained using the resin composition.

Background

As a manufacturing technique of a printed wiring board, a manufacturing method based on a stack (build) method of alternately overlapping insulating layers and conductor layers is known.

As an insulating material for a printed wiring board that can be used for such an insulating layer, for example, patent document 1 discloses a resin composition.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open No. 2019 and 6869.

Disclosure of Invention

Problems to be solved by the invention

In recent years, further improvement in the dielectric constant of an insulating layer has been demanded. Further, with the spread of smart phones and the like, the demand for thinner devices is increasing, and therefore thinner insulating layers are demanded. When the insulating layer is thin, warpage tends to occur, and therefore, it is required to suppress the cure shrinkage of the insulating layer.

The subject of the invention is to provide: a resin composition which can suppress the curing shrinkage and can give a cured product having an excellent dielectric constant; a resin sheet comprising the resin composition; a printed wiring board and a semiconductor device are provided with an insulating layer formed by using the resin composition.

Means for solving the technical problem

The present inventors have made diligent studies on the above problems, and as a result, have found that: the above object can be achieved by containing (a) a compound having an aromatic ester skeleton and an unsaturated bond and (B) a predetermined amount of a polyimide resin, and the present invention has been completed.

That is, the present invention includes the following items,

[1] a resin composition comprising the following components (A) and (B),

(A) a compound having an aromatic ester skeleton and an unsaturated bond,

(B) A polyimide resin,

wherein the content of the component (B) is 10 to 50 mass% based on 100 mass% of nonvolatile components in the resin composition;

[2] the resin composition according to [1], wherein the component (A) is any of a compound represented by the following general formula (A-1) and a compound represented by the following general formula (A-2),

[ chemical formula 1]

(in the general formula (A-1), Ar¹¹Each independently represents a monovalent aromatic hydrocarbon group optionally having a substituent, Ar¹²Each independently represents a divalent aromatic hydrocarbon group optionally having a substituent, Ar¹³Each independently represents a divalent aromatic hydrocarbon group optionally having a substituent, a divalent aliphatic hydrocarbon group optionally having a substituent, an oxygen atom, a sulfur atom, or a divalent group formed by combining these groups. n represents an integer of 0 to 10. )

[ chemical formula 2]

(in the general formula (A-2), Ar²¹Represents an optionally substituted m-valent aromatic hydrocarbon group, Ar²²Each independently represents a monovalent aromatic hydrocarbon group optionally having a substituent. m represents an integer of 2 or 3. )

[3] The resin composition according to [1] or [2], wherein the content of the component (A) is 0.1 to 30 mass% based on 100 mass% of nonvolatile components in the resin composition;

[4] the resin composition according to any one of [1] to [3], further comprising (C) an inorganic filler;

[5] the resin composition according to [4], wherein the content of the component (C) is 30% by mass or more, assuming that the nonvolatile content in the resin composition is 100% by mass;

[6] the resin composition according to any one of [1] to [5], further comprising (D) a thermosetting resin;

[7] the resin composition according to any one of [1] to [6], which is used for forming an insulating layer;

[8] the resin composition according to any one of [1] to [7], which is used for forming an insulating layer for forming a conductor layer;

[9] a resin sheet, comprising:

support body, and

a resin composition layer comprising the resin composition according to any one of [1] to [8] provided on the support;

[10] a printed wiring board comprising an insulating layer formed from a cured product of the resin composition according to any one of [1] to [8 ];

[11] a multilayer flexible substrate comprising an insulating layer formed of a cured product of the resin composition according to any one of [1] to [8 ];

[12] a semiconductor device comprising the printed wiring board of [10 ];

[13] a semiconductor device comprising the multilayer flexible substrate according to [11 ].

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a resin composition which can suppress the curing shrinkage and can give a cured product having an excellent dielectric constant; a resin sheet comprising the resin composition; a printed wiring board, a multilayer flexible substrate and a semiconductor device are provided with an insulating layer formed by using the resin composition.

Drawings

Fig. 1 is a schematic view showing an example of a resin sheet in measurement of a curing shrinkage rate.

Detailed Description

The present invention will be described in detail below with reference to preferred embodiments thereof. However, the present invention is not limited to the embodiments and examples described below, and can be implemented by arbitrarily changing the embodiments without departing from the scope of the claims and the equivalent scope thereof. The dielectric constant is a relative dielectric constant unless otherwise specified.

[ resin composition ]

The resin composition of the present invention is a resin composition containing (a) a compound having an aromatic ester skeleton and an unsaturated bond and (B) a polyimide resin, and the content of the component (B) is 10 mass% or more and 50 mass% or less, assuming that the nonvolatile content in the resin composition is 100 mass%. In the present invention, by containing the component (a) and further containing the component (B) in a predetermined amount, the cure shrinkage can be suppressed, and a cured product having an excellent dielectric constant can be obtained. In addition, a cured product having an excellent dielectric loss tangent can be obtained.

The resin composition may further contain an optional component in combination with the components (a) to (B). Examples of the optional components include (C) an inorganic filler, (D) a thermoplastic resin, (E) a curing accelerator, and (F) other additives. Hereinafter, each component contained in the resin composition will be described in detail.

< (A) A Compound having an aromatic ester skeleton and an unsaturated bond

The resin composition contains, as the component (A), a compound (A) having an aromatic ester skeleton and an unsaturated bond. By containing the component (A) in the resin composition, the curing shrinkage can be suppressed, and a cured product having an excellent dielectric constant can be obtained. (A) One kind of the component may be used alone, or two or more kinds may be used in combination.

(A) The component (A) has an aromatic ester skeleton. The aromatic ester skeleton means a skeleton having an ester bond and an aromatic ring bonded to one or both ends of the ester bond. Among them, it is preferable that the ester bond has aromatic rings at both ends. Examples of the group having such a skeleton include arylcarbonyloxy, aryloxycarbonyl, arylcarbonyloxyarylene, aryloxycarbonylarylene, arylcarbonyloxyarylene, aryloxycarbonyloxyarylene, and aryloxycarbonyrylene. The number of carbon atoms of the group having such a skeleton is preferably 7 to 20, more preferably 7 to 15, further preferably 7 to 11. The aromatic hydrocarbon group such as an aryl group and an arylene group may have a substituent.

The aryl group is preferably an aryl group having 6 to 30 carbon atoms, more preferably an aryl group having 6 to 20 carbon atoms, and still more preferably an aryl group having 6 to 10 carbon atoms. Examples of such aryl groups include groups obtained by removing 1 hydrogen atom from a monocyclic aromatic compound, such as phenyl, furyl, pyrrolyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, and triazinyl; and groups obtained by removing 1 hydrogen atom from a condensed ring aromatic compound such as naphthyl, anthryl, phenalenyl, phenanthryl, quinolyl, isoquinolyl, quinazolinyl, phthalazinyl, pteridinyl, oxatheanyl (coumarinyl), indolyl, benzimidazolyl, benzofuranyl, and acridinyl.

The arylene group is preferably an arylene group having 6 to 30 carbon atoms, more preferably an arylene group having 6 to 20 carbon atoms, and still more preferably an arylene group having 6 to 10 carbon atoms. Examples of such arylene groups include phenylene, naphthylene, anthrylene and biphenylene (-C)₆H₄-C₆H₄-) and the like.

(A) The component (B) contains an unsaturated bond. This results in an excellent dielectric constant of the cured product. In addition, the unsaturated bond contributes to the curing reaction of the resin composition. Since the unsaturated bond contributes to the curing reaction, an ester portion of the aromatic ester skeleton can be suppressed from being used in the curing reaction, and as a result, the curing shrinkage can be suppressed.

The unsaturated bond is preferably a carbon-carbon unsaturated bond. The unsaturated bond is preferably a substituent having at least 1 unsaturated bond. Examples of the unsaturated bond include unsaturated hydrocarbon groups such as an alkenyl group having 2 to 30 carbon atoms and an alkynyl group having 2 to 30 carbon atoms. The unsaturated bond is preferably present as a substituent of the terminal aromatic hydrocarbon group, and more preferably present as a substituent of the aromatic hydrocarbon groups at both terminals.

Examples of the alkenyl group having 2 to 30 carbon atoms include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a 1-propenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1-hexenyl group, a 2-hexenyl group, a 3-hexenyl group, a 4-hexenyl group, a 5-hexenyl group, a 1-octenyl group, a 2-octenyl group, a 1-undecenyl group, a 1-pentadecenyl group, a 3-pentadecenyl group, a 7-pentadecenyl group, a 1-octadecenyl group, a 2-octadecenyl group, a cyclopentenyl group, a cyclohexenyl group, a cyclooctenyl group, a1, 3-butadienyl group, a1, 4-butadienyl group, a1, 3-hexadienyl group, a2, 5-hexadienyl group, a 4, 7-pentadece, 1,4, 7-pentadecatrienoyl, and the like.

Examples of the alkynyl group having 2 to 30 carbon atoms include ethynyl, propynyl, 1-butynyl, 2-butynyl, 3-pentynyl, 4-pentynyl, 1, 3-butadiynyl and the like.

Among them, the unsaturated bond is preferably an alkenyl group having 2 to 30 carbon atoms, more preferably an alkenyl group having 2 to 10 carbon atoms, further preferably an alkenyl group having 2 to 5 carbon atoms, further preferably an allyl group, an isopropenyl group, or a 1-propenyl group, particularly preferably an allyl group.

(A) The component (C) may have any of an aromatic hydrocarbon group, an aliphatic hydrocarbon group, an oxygen atom, a sulfur atom, and a group formed by a combination thereof, in addition to the aromatic ester skeleton. The term "aromatic hydrocarbon group" refers to a hydrocarbon group comprising an aromatic ring, which may be any of monocyclic, polycyclic, heterocyclic rings.

The aromatic hydrocarbon group is preferably a divalent aromatic hydrocarbon group, more preferably an arylene group, an aralkylene group, and still more preferably an arylene group. The arylene group is preferably an arylene group having 6 to 30 carbon atoms, more preferably an arylene group having 6 to 20 carbon atoms, and still more preferably an arylene group having 6 to 10 carbon atoms. Examples of such arylene groups include phenylene, naphthylene, anthrylene, and biphenylene. The aralkylene group is preferably an aralkylene group having 7 to 30 carbon atoms, more preferably an aralkylene group having 7 to 20 carbon atoms, and still more preferably an aralkylene group having 7 to 15 carbon atoms. Among them, phenylene group is preferred.

The aliphatic hydrocarbon group is preferably a divalent aliphatic hydrocarbon group, more preferably a divalent saturated aliphatic hydrocarbon group, and further preferably an alkylene group or a cycloalkylene group. The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and still more preferably an alkylene group having 1 to 3 carbon atoms. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a 1-methylmethylene group, a1, 1-dimethylmethylene group, a 1-methylethylene group, a1, 1-dimethylethylene group, a1, 2-dimethylethylene group, a butylene group, a 1-methylpropylene group, a 2-methylpropylene group, a pentylene group, and a hexylene group.

The cycloalkylene group is preferably a cycloalkylene group having 3 to 20 carbon atoms, more preferably a cycloalkylene group having 3 to 15 carbon atoms, and still more preferably a cycloalkylene group having 5 to 10 carbon atoms. Examples of the cycloalkylene group include cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cyclopentylene, cycloheptylene, and cycloalkylene groups represented by the following formulae (a) to (d). In formulae (a) to (d), "+" represents a connecting bond;

[ chemical formula 3]

The aromatic ester skeleton, the aromatic hydrocarbon group, the aliphatic hydrocarbon group, and the unsaturated hydrocarbon group may have a substituent. Examples of the substituent include an unsaturated hydrocarbon group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen atom, and the like. The substituents may be contained alone or in combination of two or more.

Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a tert-pentyl group, a neopentyl group, a1, 2-dimethylpropyl group, an n-hexyl group, an isohexyl group, an n-nonyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclononyl group.

The alkoxy group having 1 to 10 carbon atoms is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a 2-ethylhexyloxy group, an octyloxy group, and a nonyloxy group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like. The above-mentioned substituent may further have a substituent (hereinafter, sometimes referred to as "secondary substituent"). The unsaturated hydrocarbon group is as described above. As the secondary substituent, the same groups as those described above may be used unless otherwise specified.

(A) The component (B) is preferably any of a compound represented by the following general formula (A-1) and a compound represented by the following general formula (A-2);

[ chemical formula 4]

(in the general formula (A-1), Ar¹¹Each independently represents a monovalent aromatic hydrocarbon group optionally having a substituent, Ar¹²Each independently represents a divalent aromatic hydrocarbon group optionally having a substituent, Ar¹³Each independently represents a divalent aromatic hydrocarbon group optionally having a substituent, a divalent aliphatic hydrocarbon group optionally having a substituent, an oxygen atom, a sulfur atom, or a divalent group formed by a combination thereof. n represents an integer of 0 to 10. )

[ chemical formula 5]

(in the general formula (A-2), Ar²¹Represents an optionally substituted m-valent aromatic hydrocarbon group, Ar²²Each independently represents a monovalent aromatic hydrocarbon group optionally having a substituent. m represents an integer of 2 or 3. ).

In the general formula (A-1), Ar¹¹Each independently represents a monovalent aromatic hydrocarbon group optionally having a substituent. Examples of the monovalent aromatic hydrocarbon group include groups obtained by removing 1 hydrogen atom from a monocyclic aromatic compound, such as a phenyl group, a furyl group, a pyrrolyl group, a thienyl group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group, an isothiazolyl group, a pyridyl group, a pyrimidinyl group, a pyridazinyl group, a pyrazinyl group, and a triazinyl group; and groups obtained by removing 1 hydrogen atom from a condensed ring aromatic compound, such as naphthyl, anthryl, phenalkenyl, phenanthryl, quinolyl, isoquinolyl, quinazolinyl, phthalazinyl, pteridinyl, oxatheaphthonyl, indolyl, benzimidazolyl, benzofuranyl, and acridinyl, and among them, a phenyl group is preferable from the viewpoint of remarkably obtaining the effects of the present invention. Ar (Ar)¹¹The monovalent aromatic hydrocarbon group represented by (a) optionally has a substituent. The substituents are the same as those optionally contained in the aromatic ester skeleton. Wherein Ar is¹¹The substituent(s) preferably contains an unsaturated bond.

In the general formula (A-1), Ar¹²Each independently represents a divalent aromatic hydrocarbon group optionally having a substituent. The divalent aromatic hydrocarbon group includes an arylene group, an aralkylene group and the like, and an arylene group is preferred. The arylene group is preferably an arylene group having 6 to 30 carbon atoms, more preferably an arylene group having 6 to 20 carbon atoms, and still more preferably an arylene group having 6 to 10 carbon atoms. Examples of such arylene groups include phenylene, naphthylene, anthrylene, and biphenylene. The aralkylene group is preferably an aralkylene group having 7 to 30 carbon atoms, more preferably an aralkylene group having 7 to 20 carbon atoms, and still more preferably an aralkylene group having 7 to 15 carbon atoms. Among them, phenylene group is preferred.

Ar¹²The divalent aromatic hydrocarbon group represented by (a) optionally has a substituent. The substituents are the same as those optionally contained in the aromatic ester skeleton.

In the general formula (A-1), Ar¹³Each independently represents a divalent aromatic hydrocarbon group optionally having a substituent, a divalent aliphatic hydrocarbon group optionally having a substituent, an oxygen atom, a sulfur atom, or a divalent group composed of a combination thereof, preferably a divalent group composed of a combination thereof. As a divalent aromatic hydrocarbon radical, with Ar¹²The divalent aromatic hydrocarbon groups represented are the same.

The divalent aliphatic hydrocarbon group is more preferably a divalent saturated aliphatic hydrocarbon group, and is preferably an alkylene group or a cycloalkylene group, more preferably a cycloalkylene group.

The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and still more preferably an alkylene group having 1 to 3 carbon atoms. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a 1-methylmethylene group, a1, 1-dimethylmethylene group, a 1-methylethylene group, a1, 1-dimethylethylene group, a1, 2-dimethylethylene group, a butylene group, a 1-methylpropylene group, a 2-methylpropylene group, a pentylene group, and a hexylene group.

The cycloalkylene group is preferably a cycloalkylene group having 3 to 20 carbon atoms, more preferably a cycloalkylene group having 3 to 15 carbon atoms, and still more preferably a cycloalkylene group having 5 to 10 carbon atoms. Examples of the cycloalkylene group include cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cyclopentylene, cycloheptylene, and cycloalkylene groups represented by the above formulae (a) to (d), and the cycloalkylene group represented by the formula (c) is preferred.

The divalent group formed by combining these groups is preferably a divalent group formed by combining a divalent aromatic hydrocarbon group optionally having a substituent and a divalent aliphatic hydrocarbon group optionally having a substituent, and more preferably a divalent group formed by alternately combining a plurality of divalent aromatic hydrocarbon groups optionally having a substituent and a plurality of divalent aliphatic hydrocarbon groups optionally having a substituent. Specific examples of the divalent group include the following divalent groups (A1) to (A8). In the formula, a1 to a8 each represents an integer of 0 to 10, preferably 0 to 5. "+" represents a connecting bond, and a wavy line represents a structure obtained by reacting an aromatic compound, an acid halide of an aromatic compound, or an ester of an aromatic compound, which is used in the synthesis of the component (A);

[ chemical formula 6]

[ chemical formula 7]

Ar¹³The divalent aromatic hydrocarbon group and the divalent aliphatic hydrocarbon group represented by (a) are optionally substituted. The substituents are the same as those optionally contained in the aromatic ester skeleton.

In the general formula (A-1), n represents an integer of 0 to 10, preferably 0 to 5, more preferably 0 to 3. When the compound represented by the general formula (A-1) is an oligomer or a polymer, n represents the average value thereof.

In the general formula (A-2), Ar²¹Represents an m-valent aromatic hydrocarbon group which may have a substituent. The m-valent aromatic hydrocarbon group is preferably an m-valent aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an m-valent aromatic hydrocarbon group having 6 to 20 carbon atoms, and still more preferably an m-valent aromatic hydrocarbon group having 6 to 10 carbon atomsA hydrocarbyl group. Ar (Ar)²¹The m-valent aromatic hydrocarbon group represented by (a) optionally has a substituent. The substituents are the same as those optionally contained in the aromatic ester skeleton.

In the general formula (A-2), Ar²²Each independently represents a monovalent aromatic hydrocarbon group optionally having a substituent. Ar (Ar)²²With Ar in the general formula (A-1)¹¹The aromatic hydrocarbon groups represented are the same. Ar (Ar)²²The monovalent aromatic hydrocarbon group represented by (a) optionally has a substituent. The substituents are the same as those optionally contained in the aromatic ester skeleton.

In the general formula (A-2), m represents an integer of 2 or 3, preferably 2.

Specific examples of the component (A) include the following compounds. Specific examples of the component (A) include compounds described in paragraphs 0068 to 0071 of International publication No. 2018/235424 and paragraphs 0113 to 0115 of International publication No. 2018/235425. However, the component (A) is not limited to these specific examples. Wherein s represents an integer of 0 or 1 or more, and r represents an integer of 1 to 10;

[ chemical formula 8]

(A) The component (C) may be a compound synthesized by a known method. (A) The synthesis of the component (a) can be carried out by, for example, the method described in International publication No. 2018/235424 or International publication No. 2018/235425.

From the viewpoint of remarkably obtaining the effect of the present invention, the weight average molecular weight of the component (a) is preferably 150 or more, more preferably 200 or more, further preferably 250 or more, preferably 3000 or less, more preferably 2000 or less, further preferably 1500 or less. (A) The weight average molecular weight of the component (a) is a weight average molecular weight in terms of polystyrene measured by a Gel Permeation Chromatography (GPC) method.

From the viewpoint of remarkably obtaining the effect of the present invention, the unsaturated bond equivalent of the component (A) is preferably 50g/eq or more, more preferably 100g/eq or more, further preferably 150g/eq or more, preferably 2000g/eq or less, further preferably 1000g/eq or less, further preferably 500g/eq or less. The unsaturated bond equivalent is the mass of the (a) component containing 1 equivalent of unsaturated bonds.

The content of the component (a) is 0.1 mass% or more, preferably 1 mass% or more, more preferably 3 mass% or more, and the content of the component (a) is 30 mass% or less, preferably 28 mass% or less, further preferably 25 mass% or less, 20 mass% or less, 15 mass% or less, or 10 mass% or less, based on 100 mass% of nonvolatile components in the resin composition, from the viewpoint that the cure shrinkage can be suppressed and a cured product having an excellent dielectric constant can be obtained.

(B) polyimide resin

The resin composition contains (B) a polyimide resin as the component (B). By containing the component (B) in the resin composition, a cured product thereof becomes flexible, and as a result, the curing shrinkage can be suppressed, and a cured product having an excellent dielectric constant can be obtained.

From the viewpoint of suppressing the curing shrinkage, the content of the component (B) is 10 mass% or more, preferably 13 mass% or more, more preferably 15 mass% or more, and further preferably 20 mass% or more, assuming that the nonvolatile content in the resin composition is 100 mass%. From the viewpoint of remarkably obtaining the desired effect of the present invention, the upper limit is 50 mass% or less, preferably 40 mass% or less, more preferably 30 mass% or less, and further preferably 25 mass% or less.

(B) The component (c) is not particularly limited as long as it is a resin having an imide bond in a repeating unit. (B) The component (B) generally includes a diamine compound obtained by imidization of an acid anhydride. (B) The component (C) further contains a modified polyimide resin such as a siloxane-modified polyimide resin. (B) One kind of the component may be used alone, or two or more kinds may be used in combination.

The diamine compound used for producing the component (B) is not particularly limited, and examples thereof include aliphatic diamine compounds and aromatic diamine compounds.

Examples of the aliphatic diamine compound include linear aliphatic diamine compounds such as 1, 2-ethylenediamine, 1, 2-diaminopropane, 1, 3-diaminopropane, 1, 4-diaminobutane, 1, 6-hexamethylenediamine, 1, 5-diaminopentane, and 1, 10-diaminodecane; branched aliphatic diamine compounds such as 1, 2-diamino-2-methylpropane, 2, 3-diamino-2, 3-butane and 2-methyl-1, 5-diaminopentane; alicyclic diamine compounds such as 1, 3-bis (aminomethyl) cyclohexane, 1, 4-diaminocyclohexane, and 4,4' -methylenebis (cyclohexylamine); dimer acid-based diamines (hereinafter also referred to as "dimer diamines") and the like, and among them, dimer acid-based diamines are preferred.

The dimer acid type diamine refers to dimer acid having two terminal carboxylic acid groups (-COOH) substituted by aminomethyl (-CH)₂-NH₂) Or amino (-NH)₂) A diamine compound obtained by substitution. The dimer acid is a known compound obtained by dimerizing an unsaturated fatty acid (preferably, an unsaturated fatty acid having 11 to 22 carbon atoms, particularly preferably, an unsaturated fatty acid having 18 carbon atoms), and its industrial production process is generally standardized in the industry. The dimer acid is easily obtained, in particular, from a dimer acid containing 36 carbon atoms, which is obtained by dimerizing an unsaturated fatty acid having 18 carbon atoms such as oleic acid or linoleic acid, which is inexpensive and easily available, as a main component. Further, the dimer acid may contain a monomer acid, a trimer acid, other polymerized fatty acid, and the like in an arbitrary amount depending on the production method, the degree of purification, and the like. In addition, although a double bond remains after the polymerization reaction of the unsaturated fatty acid, in the present specification, a hydride which is further hydrogenated to reduce the degree of unsaturation is also included in the dimer acid. Commercially available dimer acid type diamines include, for example, "PRIAMINE 1073", "PRIAMINE 1074" and "PRIAMINE 1075" manufactured by Croda Japan; "VERSAME 551" and "VERSAMINE 552" manufactured by Cognis Japan, Inc.

Examples of the aromatic diamine compound include a phenylenediamine compound, a naphthalenediamine compound, and a diphenylamine compound.

The phenylenediamine compound is a compound formed of a benzene ring having 2 amino groups, and the benzene ring may optionally have 1 to 3 substituents. The substituents herein are the same as those optionally contained in the aromatic ester skeleton in the component (A). Examples of the phenylenediamine compound include 1, 4-phenylenediamine, 1, 2-phenylenediamine, 1, 3-phenylenediamine, 2, 4-diaminotoluene, 2, 6-diaminotoluene, 3, 5-diaminobiphenyl, 2,4,5, 6-tetrafluoro-1, 3-phenylenediamine, and the like.

The naphthalene diamine compound is a compound formed of a naphthalene ring having 2 amino groups, and the naphthalene ring may optionally have 1 to 3 substituents. The substituents herein are the same as those optionally contained in the aromatic ester skeleton in the component (A). Examples of the naphthalenediamine compound include 1, 5-diaminonaphthalene, 1, 8-diaminonaphthalene, 2, 6-diaminonaphthalene, and 2, 3-diaminonaphthalene.

The diphenylamine compound is a compound having 2 aniline structures in a molecule, and 2 benzene rings in each of the 2 aniline structures may optionally have 1 to 3 substituents. The substituents herein are the same as those optionally contained in the aromatic ester skeleton in the component (A). The 2 aniline structures in the diphenylamine compound may be bonded directly and/or via 1 or 2 linking (linker) structures having 1 to 100 skeleton atoms selected from carbon atoms, oxygen atoms, sulfur atoms, and nitrogen atoms. The diphenylamine compound also comprises a compound in which 2 aniline structures are bonded by 2 bonds.

Specific examples of the "linking structure" in the diphenylamine compound include-NHCO-, -CONH-, -OCO-, -COO-, -CH₂-、-CH₂CH₂-、-CH₂CH₂CH₂-、-CH₂CH₂CH₂CH₂-、-CH₂CH₂CH₂CH₂CH₂-、-CH(CH₃)-、-C(CH₃)₂-、-C(CF₃)₂-、-CH＝CH-、-O-、-S-、-CO-、-SO₂-、-NH-、-Ph-、-Ph-Ph-、-C(CH₃)₂-Ph-C(CH₃)₂-、-O-Ph-O-、-O-Ph-Ph-O-、-O-Ph-SO₂-Ph-O-、-O-Ph-C(CH₃)₂-Ph-O-、-Ph-CO-O-Ph-、-C(CH₃)₂-Ph-C(CH₃)₂-, groups represented by the following formulae (I) and (II), and groups formed by combining them. In the present specification, "Ph" represents a1, 4-phenylene group, a1, 3-phenylene group or a1, 2-phenylene group.

[ chemical formula 9]

In one embodiment, specific examples of the diphenylamine compound include 4,4 '-diamino-2, 2' -bis (trifluoromethyl) -1,1 '-biphenyl, 3,4' -diaminodiphenyl ether, 4 '-diaminodiphenyl ether, 3' -diaminodiphenyl sulfone, 4 '-diaminodiphenyl sulfide, 4-aminophenyl 4-aminobenzoate, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1, 4-bis (4-aminophenoxy) benzene, 2-bis (4-aminophenyl) propane, 4' - (hexafluoroisopropylidene) diphenylamine, and the like, 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, α -bis [4- (4-aminophenoxy) phenyl ] -1, 3-diisopropylbenzene, α -bis [4- (4-aminophenoxy) phenyl ] -1, 4-diisopropylbenzene, 4' - (9-fluorenylidene) diphenylamine, 2-bis (3-methyl-4-aminophenyl) propane, 2-bis (3-methyl-4-aminophenyl) benzene, 4' -diamino-3, 3' -dimethyl-1, 1' -biphenyl, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluorobenzene, 4' -diamino-3, 3' -dimethyl-1, 1' -biphenyl, and mixtures thereof, 4,4 '-two amino-2, 2' -two methyl-1, 1 '-biphenyl, 9' -bis (3-methyl-4-amino phenyl) fluorene, 5- (4-amino phenoxy) -3- [4- (4-amino phenoxy) phenyl ] -1,1, 3-three methyl indan, preferably 5- (4-amino phenoxy) -3- [4- (4-amino phenoxy) phenyl ] -1,1, 3-three methyl indan.

In another embodiment, the diphenylamine compound may be, for example, a diamine compound represented by the following formula (B-1).

[ chemical formula 10]

(in the formula (B-1), R¹～R⁸Each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, -X⁹-R⁹or-X¹⁰-R¹⁰，R¹～R⁸At least one of which is-X¹⁰-R¹⁰，X⁹Each independently represents a single bond, -NR^9'-、-O-、-S-、-CO-、-SO₂-、-NR^9'CO-、-CONR^9'-, -OCO-, or-COO-, R⁹Each independently represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkenyl group, R^9'Each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group, X¹⁰Each independently represents a single bond, - (substituted or unsubstituted alkylene) -, -NH-, -O-, -S-, -CO-, -SO₂-, -NHCO-, -CONH-, -OCO-, or-COO-, R¹⁰Each independently represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. ).

R in the formula (B-1)⁹And R^9'The alkyl group represented means a straight-chain, branched-chain or cyclic monovalent aliphatic saturated hydrocarbon group. The alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms. Examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, a cyclopentyl group, and a cyclohexyl group.

R in the formula (B-1)⁹And R⁹The alkenyl group represented by' means a straight-chain, branched-chain or cyclic monovalent unsaturated hydrocarbon group having at least 1 carbon-carbon double bond. The alkenyl group is preferably an alkenyl group having 2 to 6 carbon atoms, more preferably an alkenyl group having 2 or 3 carbon atoms. Examples of such alkenyl groups include vinyl, 1-propenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl, 3-methyl-2-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-methyl-3-pentenyl, 1-hexenyl, 3-hexenyl, 5-hexenyl, 2-cyclohexenyl and the like. The substituent for the alkenyl group in the "substituted or unsubstituted alkenyl group" is not particularly limited, and examples thereof include a halogen atom,cyano, alkoxy, aryl, heteroaryl, amino, nitro, hydroxy, carboxy, sulfo, and the like. The number of substituents is preferably 1 to 3, more preferably 1.

The substituent for the alkyl group in the "substituted or unsubstituted alkyl group" and the substituent for the alkenyl group in the "substituted or unsubstituted alkenyl group" are not particularly limited, and examples thereof include a halogen atom, a cyano group, an alkoxy group, an amino group, a nitro group, a hydroxyl group, a carboxyl group, and a sulfo group. The number of substituents is preferably 1 to 3, more preferably 1.

Alkoxy means a monovalent group (alkyl-O-) formed by bonding an alkyl group to an oxygen atom. The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably an alkoxy group having 1 to 3 carbon atoms. Examples of such an alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, and a pentyloxy group.

X in the formula (B-1)¹⁰The alkylene group is a linear, branched or cyclic divalent aliphatic saturated hydrocarbon group, preferably an alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms. Examples of the alkylene group include-CH₂-、-CH₂-CH₂-、-CH(CH₃)-、-CH₂-CH₂-CH₂-、-CH₂-CH(CH₃)-、-CH(CH₃)-CH₂-、-C(CH₃)₂-、-CH₂-CH₂-CH₂-CH₂-、-CH₂-CH₂-CH(CH₃)-、-CH₂-CH(CH₃)-CH₂-、-CH(CH₃)-CH₂-CH₂-、-CH₂-C(CH₃)₂-、-C(CH₃)₂-CH₂-and the like. The substituent of the alkylene group in the "substituted or unsubstituted alkylene group" is not particularly limited, and examples thereof include a halogen atom, a cyano group, an alkoxy group, an aryl group, a heteroaryl group, an amino group, a nitro group, a hydroxyl group, a carboxyl group, a sulfo group and the like. The number of substituents is preferably 1 to 3, more preferably 1.

As R in the formula (B-1)¹⁰Aryl radical ofThe aryl group is preferably an aryl group having 6 to 14 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms. Examples of such aryl groups include phenyl, 1-naphthyl and 2-naphthyl groups, with phenyl being preferred. The substituent for the aryl group in the "substituted or unsubstituted aryl group" is not particularly limited, and examples thereof include a halogen atom, a cyano group, an alkyl group, an alkoxy group, an aryl group, a heteroaryl group, an amino group, a nitro group, a hydroxyl group, a carboxyl group, and a sulfo group. The number of substituents is preferably 1 to 3, more preferably 1.

R in the formula (B-1)¹⁰The heteroaryl group represented means an aromatic heterocyclic group having 1 to 4 hetero atoms selected from an oxygen atom, a nitrogen atom and a sulfur atom. The heteroaryl group is preferably a 5-to 12-membered (preferably 5-or 6-membered) monocyclic, bicyclic or tricyclic (preferably monocyclic) aromatic heterocyclic group. Examples of such heteroaryl groups include furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, 1,2, 3-oxadiazolyl, 1,2, 4-oxadiazolyl, 1,3, 4-oxadiazolyl, furazanyl, 1,2, 3-thiadiazolyl, 1,2, 4-thiadiazolyl, 1,3, 4-thiadiazolyl, 1,2, 3-triazolyl, 1,2, 4-triazolyl, tetrazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, and the like. The substituent for the heteroaryl group in the "substituted or unsubstituted heteroaryl group" is the same as the substituent for the aryl group in the "substituted or unsubstituted aryl group".

R¹～R⁸Each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, -X⁹-R⁹or-X¹⁰-R¹⁰。R¹～R⁸Preferably each independently a hydrogen atom, or-X¹⁰-R¹⁰。

R¹～R⁸At least one of which is-X¹⁰-R¹⁰. Preferably R is¹～R⁸One or two of them is-X¹⁰-R¹⁰More preferably R⁵～R⁸One or two of them is-X¹⁰-R¹⁰Further preferably R⁵And R⁷One or two of them is-X¹⁰-R¹⁰。

In a fruitIn the embodiment, R is preferred¹～R⁸One or two of them is-X¹⁰-R¹⁰And R is¹～R⁸The others of (A) are hydrogen atoms, more preferably R⁵～R⁸One or two of them is-X¹⁰-R¹⁰And R is¹～R⁸The others in (A) are hydrogen atoms, more preferably R⁵And R⁷One or two of them is-X¹⁰-R¹⁰And R is¹～R⁸The others of (a) are hydrogen atoms.

X⁹Each independently represents a single bond, -NR^9'-、-O-、-S-、-CO-、-SO₂-、-NR^9'CO-、-CONR^9'-, -OCO-, or-COO-. R⁹Each independently represents a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group. X⁹Preferably a single bond.

R^9'Each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group. R⁹Preferred is a substituted or unsubstituted alkyl group.

X¹⁰Each independently represents a single bond, - (substituted or unsubstituted alkylene) -, -NH-, -O-, -S-, -CO-, -SO₂-, -NHCO-, -CONH-, -OCO-, or-COO-. X¹⁰Preferably a single bond.

R¹⁰Each independently represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. R¹⁰Substituted or unsubstituted aryl groups are preferred.

In one embodiment, the diamine compound represented by the formula (B-1) is preferably a compound represented by the following formula (B-2), more preferably a compound represented by the following formula (B-3) (5-amino-1, 1' -biphenyl-2-yl 4-aminobenzoate);

[ chemical formula 11]

(in the formula, R¹～R⁶And R⁸Each independently represents a hydrogen atom or a halogenAtom, cyano, nitro, -X⁹-R⁹The other symbols have the same meanings as in the formula (B-1). )

[ chemical formula 12]

The diamine compound may be a commercially available product or a compound synthesized by a known method. For example, the diamine compound represented by the formula (B-1) can be synthesized by the synthesis method described in Japanese patent No. 6240798 or a method based thereon. One kind of diamine compound may be used alone, or two or more kinds may be used in combination.

The acid anhydride used for preparing the (B) component is not particularly limited, but in a preferred embodiment, the acid anhydride is aromatic tetracarboxylic dianhydride. Examples of the aromatic tetracarboxylic acid dianhydride include pyromellitic acid dianhydride, naphthalene tetracarboxylic acid dianhydride, anthracene tetracarboxylic acid dianhydride, and bisphthalic acid dianhydride, with bisphthalic acid dianhydride being preferred.

The pyromellitic dianhydride is a dianhydride of benzene having 4 carboxyl groups, and the benzene ring herein may optionally have 1 to 3 substituents. Here, as the substituent, it is preferably selected from the group consisting of a halogen atom, a cyano group, and-X¹³-R¹³(the same as defined in the following formula (B-4)). Specific examples of the pyromellitic dianhydride include pyromellitic dianhydride and 1,2,3, 4-pyromellitic dianhydride.

The naphthalene tetracarboxylic dianhydride is a dianhydride of naphthalene having 4 carboxyl groups, and the naphthalene ring herein may optionally have 1 to 3 substituents. Here, as the substituent, it is preferably selected from the group consisting of a halogen atom, a cyano group, and-X¹³-R¹³(the same as defined in the following formula (B-4)). Specific examples of the naphthalene tetracarboxylic dianhydride include 1,4,5, 8-naphthalene tetracarboxylic dianhydride, and 2,3,6, 7-naphthalene tetracarboxylic dianhydride.

The anthracene tetracarboxylic dianhydride is an anthracene dianhydride having 4 carboxyl groups, and an anthracene ring herein may optionally have 1 to 3 substituents. Here, theAs the substituent, it is preferably selected from the group consisting of a halogen atom, a cyano group, and-X¹³-R¹³(the same as defined in the following formula (B-4)). Specific examples of the anthracenetetracarboxylic dianhydride include 2,3,6, 7-anthracenetetracarboxylic dianhydride and the like.

The bisphthalic dianhydride is a compound containing 2 phthalic anhydrides in the molecule, and further 2 benzene rings of 2 phthalic anhydrides may have 1 to 3 substituents, respectively. Here, as the substituent, it is preferably selected from the group consisting of a halogen atom, a cyano group, and-X¹³-R¹³(the same as defined in the following formula (B-4)). The 2 phthalic anhydrides in the diphthalic dianhydride may be bonded directly or via a linking structure having 1 to 100 skeleton atoms selected from carbon atoms, oxygen atoms, sulfur atoms and nitrogen atoms.

Examples of the diphthalic dianhydride include compounds represented by the formula (B-4),

[ chemical formula 13]

(in the formula, R¹¹And R¹²Each independently represents a halogen atom, a cyano group, a nitro group, or-X¹³-R¹³，

X¹³Each independently represents a single bond, -NR^13'-、-O-、-S-、-CO-、-SO₂-、-NR^13'CO-、-CONR^13'-, -OCO-, or-COO-,

R¹³each independently represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkenyl group,

R^13'each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group,

y represents a single bond or a connecting structure having 1 to 100 skeleton atoms selected from a carbon atom, an oxygen atom, a sulfur atom and a nitrogen atom,

n1 and m1 each independently represent an integer of 0 to 3. ).

Y preferably has a connecting structure of 1 to 100 skeleton atoms selected from carbon atoms, oxygen atoms, sulfur atoms and nitrogen atoms. n1 and m1 are preferably 0.

The "linking structure" in Y has 1 to 100 skeleton atoms selected from carbon atoms, oxygen atoms, sulfur atoms and nitrogen atoms. The "linking structure" is preferably- [ A-Ph ]]_a-A-[Ph-A]_b- [ wherein A each independently represents a single bond, - (substituted or unsubstituted alkylene) -, -O-, -S-, -CO-, -SO₂-, -CONH-, -NHCO-, -COO-, or-OCO-, a and b each independently represent an integer of 0 to 2 (preferably 0 or 1). The (a) represents a divalent group.

Specific examples of the "linking structure" in Y include-CH₂-、-CH₂CH₂-、-CH₂CH₂CH₂-、-CH₂CH₂CH₂CH₂-、-CH₂CH₂CH₂CH₂CH₂-、-CH(CH₃)-、-C(CH₃)₂-、-O-、-CO-、-SO₂-、-Ph-、-O-Ph-O-、-O-Ph-SO₂-Ph-O-、-O-Ph-C(CH₃)₂-Ph-O-, etc.

Specific examples of the bisphthalic dianhydride include 3,3',4,4' -benzophenone tetracarboxylic dianhydride, 3,3',4,4' -diphenyl ether tetracarboxylic dianhydride, 3,3',4,4' -diphenylsulfone tetracarboxylic dianhydride, 3,3',4,4' -biphenyl tetracarboxylic dianhydride, 2',3,3' -biphenyl tetracarboxylic dianhydride, 2,3,3',4' -benzophenone tetracarboxylic dianhydride, 2,3,3',4' -diphenyl ether tetracarboxylic dianhydride, 2,3,3',4' -diphenylsulfone tetracarboxylic dianhydride, 2 '-bis (3, 4-dicarboxyphenoxyphenyl) sulfone dianhydride, methylene-4, 4' -bisphthalic dianhydride, and, 1, 1-ethynylene (ethylidene) -4,4 '-biphthalic dianhydride, 2-propylene (propylidene) -4,4' -biphthalic dianhydride, 1, 2-ethylene-4, 4 '-biphthalic dianhydride, 1, 3-trimethylene-4, 4' -biphthalic dianhydride, 1, 4-tetramethylene-4, 4 '-biphthalic dianhydride, 1, 5-pentamethylene-4, 4' -biphthalic dianhydride, 1, 3-bis (3, 4-dicarboxyphenyl) benzene dianhydride, 1, 4-bis (3, 4-dicarboxyphenyl) benzene dianhydride, 1, 3-bis (3, 4-dicarboxyphenoxy) benzene dianhydride, 1, 4-bis (3, 4-dicarboxyphenoxy) benzene dianhydride, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, 4'- (4,4' -isopropylidenediphenoxy) diphthalic dianhydride, and the like.

The aromatic tetracarboxylic dianhydride may be commercially available, or may be synthesized by a known method or a method based on the known method. The aromatic tetracarboxylic acid dianhydride may be used alone or in combination of two or more.

In one embodiment, the acid anhydride used for producing the component (B) may contain other acid anhydrides in addition to the aromatic tetracarboxylic dianhydride.

Specific examples of the other acid anhydrides include 1,2,3, 4-cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexane-1, 2,3, 4-tetracarboxylic dianhydride, cyclohexane-1, 2,4, 5-tetracarboxylic dianhydride, 3',4,4' -dicyclohexyltetracarboxylic dianhydride, carbonyl-4, 4 '-bis (cyclohexane-1, 2-dicarboxylic acid) dianhydride, methylene-4, 4' -bis (cyclohexane-1, 2-dicarboxylic acid) dianhydride, 1, 2-ethylene-4, 4 '-bis (cyclohexane-1, 2-dicarboxylic acid) dianhydride, oxy-4, 4' -bis (cyclohexane-1, 2-dicarboxylic acid) dianhydride, thio-4, aliphatic tetracarboxylic acid dianhydrides such as 4 '-bis (cyclohexane-1, 2-dicarboxylic acid) dianhydride and sulfonyl-4, 4' -bis (cyclohexane-1, 2-dicarboxylic acid) dianhydride.

The content of the structure derived from the aromatic tetracarboxylic dianhydride in the entire structure of the acid anhydride constituting the component (B) is preferably 10 mol% or more, more preferably 30 mol% or more, further preferably 50 mol% or more, further more preferably 70 mol% or more, further more preferably 90 mol% or more, particularly preferably 100 mol%.

(B) The component (B) is preferably a compound having a structural unit represented by the following general formula (B);

[ chemical formula 14]

(in the general formula (B), R⁵¹Represents a single bond or a residue derived from an acid anhydride, R⁵²Represents a single bond or is derived from a diamine compoundResidue of (a) or (b). ).

R⁵¹Represents a single bond or a residue derived from an acid anhydride, preferably a residue derived from an acid anhydride. R⁵¹The residue derived from an acid anhydride represented herein means a divalent group obtained by removing 2 oxygen atoms from an acid anhydride. As regards the anhydrides, the same is as mentioned above.

R⁵²Represents a single bond or a residue derived from a diamine compound, preferably a residue derived from a diamine compound. R⁵²The residue derived from the diamine compound means a divalent group obtained by removing 2 amino groups from the diamine compound. The diamine compound is as described above.

(B) The component (C) can be produced by a conventionally known method. Examples of the known method include a method in which a mixture of a diamine compound, an acid anhydride, and a solvent is heated and reacted. The amount of the diamine compound to be mixed is usually 0.5 to 1.5 molar equivalents, preferably 0.9 to 1.1 molar equivalents, based on the acid anhydride, for example.

Examples of the solvent usable for the preparation of component (B) include amide solvents such as N, N-dimethylacetamide, N-diethylacetamide, N-dimethylformamide, and N-methyl-2-pyrrolidone; ketone solvents such as acetone, Methyl Ethyl Ketone (MEK), and cyclohexanone; ester solvents such as γ -butyrolactone; hydrocarbon solvents such as cyclohexane and methylcyclohexane. In the preparation of component (B), an imidization catalyst, an azeotropic dehydration solvent, an acid catalyst, and the like may be used as necessary. Examples of the imidization catalyst include tertiary amines such as triethylamine, triisopropylamine, triethylenediamine, N-methylpyrrolidine, N-ethylpyrrolidine, N-dimethyl-4-aminopyridine, and pyridine. Examples of the azeotropic dehydration solvent include toluene, xylene, and ethylcyclohexane. Examples of the acid catalyst include acetic anhydride. The amount of the imidization catalyst, azeotropic dehydration solvent, acid catalyst and the like to be used can be appropriately set by those skilled in the art. The reaction temperature for preparing the component (B) is usually 100 to 250 ℃.

The weight average molecular weight of the component (B) is preferably 1000 or more, more preferably 5000 or more, further preferably 10000 or more, preferably 100000 or less, further preferably 70000 or less, further preferably 50000 or less.

When the content of the component (A) is represented by a1 when the nonvolatile content in the resin composition is 100% by mass and the content of the component (B) when the nonvolatile content in the resin composition is 100% by mass is represented by B1, a1/B1 is preferably 0.1 or more, more preferably 0.15 or more, still more preferably 0.2 or more, still more preferably 1 or less, still more preferably 0.5 or less, and still more preferably 0.3 or less. By making the adjustment so that a1/b1 is within the range, the effects of the present invention can be obtained remarkably.

(C) inorganic filler

The resin composition may contain, as optional components, an inorganic filler as the component (C) in addition to the above components.

As a material of the inorganic filler, an inorganic compound is used. Examples of the material of the inorganic filler include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate, zirconium phosphate, zirconium phosphotungstate, and the like. Among them, silica is particularly preferable. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica and the like. Further, spherical silica is preferable as silica. (C) The inorganic filler may be used alone or in combination of two or more.

Examples of commercially available products of component (C) include: "UFP-30" manufactured by Denka corporation; "SP 60-05" and "SP 507-05" manufactured by Nissi iron-alloy materials Corp; "YC 100C", "YA 050C", "YA 050C-MJE", "YA 010C" manufactured by Admatech (Admatech); "Silfil (シルフィル) NSS-3N", "Silfil NSS-4N", "Silfil NSS-5N" manufactured by Deshan (Tokuyama); "SC 2500 SQ", "SO-C4", "SO-C2" and "SO-C1" manufactured by Yadama corporation; and the like.

The specific surface area of the component (C) is preferably 1m²More than g, preferably 2m²More than g, particularly preferably 3m²More than g. The upper limit is not particularly limited, but is preferably 60m²Less than 50 m/g²Less than or equal to 40 m/g²The ratio of the carbon atoms to the carbon atoms is less than g. The specific surface area can be obtained by adsorbing nitrogen gas onto the surface of a sample by the BET method using a specific surface area measuring apparatus (Macsorb HM-1210, manufactured by Mountech corporation) and calculating the specific surface area by the BET multipoint method.

From the viewpoint of remarkably obtaining the desired effect of the present invention, the average particle size of the component (C) is preferably 0.01 μm or more, more preferably 0.05 μm or more, particularly preferably 0.1 μm or more, more preferably 5 μm or less, still more preferably 2 μm or less, and still more preferably 1 μm or less.

(C) The average particle diameter of the component 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 measured on a volume basis by a laser diffraction scattering particle size distribution measuring apparatus, and the median particle size is measured as an average particle size. As the measurement sample, a sample obtained by weighing 100mg of the inorganic filler and 10g of methyl ethyl ketone in a vial and dispersing them by ultrasonic waves for 10 minutes can be used. For the measurement sample, a laser diffraction type particle size distribution measuring apparatus was used, and the volume-based particle size distribution of the component (C) was measured in a flow cell (flowcell) manner using blue and red light source wavelengths, and the average particle size was calculated from the obtained particle size distribution as a median particle size. Examples of the laser diffraction type particle size distribution measuring apparatus include "LA-960" manufactured by horiba, Ltd.

From the viewpoint of improving moisture resistance and dispersibility, component (C) is preferably treated with a surface-treating agent. Examples of the surface treatment agent include vinyl silane coupling agents, (meth) acrylic acid coupling agents, fluorine-containing silane coupling agents, aminosilane coupling agents, epoxy silane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilicon nitrogen compounds, titanate coupling agents, and the like. Among them, vinyl silane-based coupling agents, (meth) acrylic acid-based coupling agents, and aminosilicone-based coupling agents are preferable from the viewpoint of remarkably obtaining the effects of the present invention. The surface treatment agent may be used alone or in combination of two or more.

Examples of commercially available surface-treating agents include "KBM 1003" (vinyltriethoxysilane), "KBM 503" (3-methacryloxypropyltriethoxysilane), and "KBM 403" (3-glycidoxypropyltrimethoxysilane), manufactured by shin-Etsu chemical Co., Ltd., "KBM 803" (3-mercaptopropyltrimethoxysilane), and "KBE 903" (3-aminopropyltriethoxysilane), manufactured by shin-Etsu chemical Co., Ltd., "KBM 573" (N-phenyl-3-aminopropyltrimethoxysilane), and "SZ-31" (hexamethyldisilazane), and "KBM 103" (phenyltrimethoxysilane), manufactured by shin-Etsu chemical Co., Ltd., "KBM-4803" (epoxy-type silane coupling agent), KBM-7103 (3,3, 3-trifluoropropyltrimethoxysilane) manufactured by shin-Etsu chemical industries, Ltd.

From the viewpoint of improving the dispersibility of the inorganic filler, it is preferable to control the degree of surface treatment with the surface treatment agent within a predetermined range. Specifically, the inorganic filler is preferably surface-treated with 0.2 to 5 parts by mass of a surface treatment agent, more preferably 0.2 to 3 parts by mass, and most preferably 0.3 to 2 parts by mass, per 100 parts by mass of the inorganic filler.

The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the carbon content per unit surface area of the inorganic filler is preferably 0.02mg/m²Above, preferably 0.1mg/m²Above, more preferably 0.2mg/m²The above. On the other hand, the melt viscosity of the resin varnish and the melt viscosity in the form of a sheet are suppressedFrom the viewpoint of the degree of increase, it is preferably 1mg/m²The concentration is preferably 0.8mg/m or less²The concentration is preferably 0.5mg/m or less²The following.

The amount of carbon per unit surface area of the inorganic filler can be measured after the inorganic filler after the surface treatment is washed with a solvent (for example, Methyl Ethyl Ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent may be added to the inorganic filler surface-treated with the surface treatment agent, and ultrasonic washing may be performed at 25 ℃ for 5 minutes. The supernatant liquid was removed, the solid components were dried, and then the amount of carbon per unit surface area of the inorganic filler material was measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by horiba, Ltd., can be used.

From the viewpoint of lowering the dielectric constant, the content of the component (C) is preferably 30% by mass or more, more preferably 40% by mass or more, further preferably 50% by mass or more, preferably 80% by mass or less, more preferably 70% by mass or less, further preferably 60% by mass or less, based on 100% by mass of nonvolatile components in the resin composition.

When the content of the component (A) when the nonvolatile content in the resin composition is 100% by mass is referred to as a1, the content of the component (B) when the nonvolatile content in the resin composition is 100% by mass is referred to as B1, and the content of the component (C) when the nonvolatile content in the resin composition is 100% by mass is referred to as C1, (a1+ B1)/C1 is preferably greater than 0.4, more preferably 0.43 or more, further preferably 0.45 or more, preferably 1 or less, further preferably 0.6 or less, further preferably 0.55 or less. By making adjustments so that (a1+ b1)/c1 is within the range, the effects of the present invention can be obtained significantly.

(D) thermosetting resin

The resin composition may contain a thermosetting resin as the component (D) as an optional component in addition to the above components. However, the components (A) to (B) are excluded. Examples of the thermosetting resin (D) include epoxy resins, phenol resins, naphthol resins, benzoxazine resins, active ester resins, cyanate ester resins, carbodiimide resins, amine resins, and acid anhydride resins. (D) One of the components may be used alone, or two or more of them may be used in combination at an arbitrary ratio. Hereinafter, resins capable of reacting with an epoxy resin to cure a resin composition, such as phenol-based resins, naphthol-based resins, benzoxazine-based resins, active ester-based resins, cyanate ester-based resins, carbodiimide-based resins, amine-based resins, and acid anhydride-based resins, may be collectively referred to as "curing agent".

Examples of the epoxy resin as the component (D) include: a biscresol (bixylenol) type epoxy resin, a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a bisphenol AF type epoxy resin, a dicyclopentadiene type epoxy resin, a trisphenol type epoxy resin, a naphthol novolac (naphthol novolac) type epoxy resin, a phenol novolac (phenol novolac) type epoxy resin, a tert-butyl-catechol type epoxy resin, a naphthalene type epoxy resin, a naphthol type epoxy resin, an anthracene type epoxy resin, a glycidylamine type epoxy resin, a glycidyl ester type epoxy resin, a cresol novolac (cresol novolac) type epoxy resin, a biphenyl type epoxy resin, a linear aliphatic epoxy resin, an epoxy resin having a butadiene structure, an alicyclic epoxy resin, a heterocyclic type epoxy resin, a spiro ring-containing epoxy resin, a cyclohexane type epoxy resin, a cyclohexane dimethanol type epoxy resin, a naphthylene ether type epoxy resin, a bisphenol S type epoxy resin, a dicyclopentadiene type epoxy resin, a naphthol type, Trimethylol type epoxy resins, tetraphenylethane type epoxy resins, and the like. The epoxy resin may be used alone or in combination of two or more.

In the resin composition, as the component (D), an epoxy resin having 2 or more epoxy groups in 1 molecule is preferably contained. From the viewpoint of remarkably obtaining the desired effect of the present invention, the proportion of the epoxy resin having 2 or more epoxy groups in 1 molecule is preferably 50% by mass or more, more preferably 60% by mass or more, particularly preferably 70% by mass or more, relative to 100% by mass of the nonvolatile component of the component (D).

The epoxy resin includes an epoxy resin that is liquid at a temperature of 20 ℃ (hereinafter, also referred to as "liquid epoxy resin") and an epoxy resin that is solid at a temperature of 20 ℃ (hereinafter, also referred to as "solid epoxy resin"). In the resin composition, as the component (D), only a liquid epoxy resin may be contained, only a solid epoxy resin may be contained, and a liquid epoxy resin and a solid epoxy resin may be contained in combination.

The liquid epoxy resin is preferably a liquid epoxy resin having 2 or more epoxy groups in 1 molecule.

The liquid epoxy resin is preferably a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a bisphenol AF type epoxy resin, a naphthalene type epoxy resin, a glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, a phenol novolac type epoxy resin, an alicyclic epoxy resin having an ester skeleton, a cyclohexane type epoxy resin, a cyclohexane dimethanol type epoxy resin, a glycidyl amine type epoxy resin, or an epoxy resin having a butadiene structure, and more preferably a bisphenol a type epoxy resin or a bisphenol F type epoxy resin.

Specific examples of the liquid epoxy resin include "HP 4032", "HP 4032D" and "HP 4032 SS" (naphthalene type epoxy resin) manufactured by DIC corporation; "828 US", "jER 828 EL", "825", "EPIKOTE 828 EL" (bisphenol A type epoxy resin) manufactured by Mitsubishi chemical company; "jER 807" and "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi chemical corporation; "jER 152" (phenol novolac type epoxy resin) manufactured by mitsubishi chemical corporation; "630" and "630 LSD" (glycidyl amine type epoxy resins) manufactured by mitsubishi chemical corporation; "ZX 1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon iron chemical Co., Ltd.; "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX; "Celloxide 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by Dailuo corporation; "PB-3600" (epoxy resin having a butadiene structure) manufactured by Dailuo corporation; "ZX 1658" and "ZX 1658 GS" (liquid 1, 4-glycidylcyclohexane-type epoxy resins) manufactured by Nippon iron chemical Co., Ltd. These may be used alone or in combination of two or more.

The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups in 1 molecule, and more preferably an aromatic solid epoxy resin having 3 or more epoxy groups in 1 molecule.

The solid epoxy resin is preferably a biphenol-type epoxy resin, a naphthalene-type tetrafunctional epoxy resin, a cresol novolak-type epoxy resin, a dicyclopentadiene-type epoxy resin, a trisphenol-type epoxy resin, a naphthol-type epoxy resin, a biphenyl-type epoxy resin, a naphthylene ether-type epoxy resin, an anthracene-type epoxy resin, a bisphenol A-type epoxy resin, a bisphenol AF-type epoxy resin, a tetraphenylethane-type epoxy resin, and more preferably a naphthalene-type epoxy resin.

The solid epoxy resin is preferably a naphthalene type tetrafunctional epoxy resin, a cresol novolak type epoxy resin, a dicyclopentadiene type epoxy resin, a trisphenol type epoxy resin, a naphthol type epoxy resin, a biphenyl type epoxy resin, a naphthylene ether type epoxy resin, an anthracene type epoxy resin, a bisphenol A type epoxy resin, a tetraphenylethane type epoxy resin, more preferably a naphthalene type tetrafunctional epoxy resin, a naphthol type epoxy resin, or a biphenyl type epoxy resin. Specific examples of the solid epoxy resin include "HP 4032H" (naphthalene type epoxy resin), "HP-4700", "HP-4710" (naphthalene type tetrafunctional epoxy resin), "N-690" (cresol novolak type epoxy resin), "N-695" (cresol novolak type epoxy resin), "HP-7200", "HP-7200 HH", "HP-7200H" (dicyclopentadiene type epoxy resin), "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S" and "HP 6000" (naphthylene ether type epoxy resin) manufactured by DIC; "EPPN-502H" (trisphenol type epoxy resin), "NC 7000L" (naphthol novolac type epoxy resin), "NC 3000H", "NC 3000L" and "NC 3100" (biphenyl type epoxy resin) manufactured by japan chemicals; ESN475V (naphthalene type epoxy resin) and ESN485 (naphthol novolac type epoxy resin) manufactured by Nippon iron chemical Co., Ltd; "YX 4000H", "YL 6121" (biphenyl type epoxy resin), "YX 4000 HK" (biphenol type epoxy resin), "YX 8800" (anthracene type epoxy resin) manufactured by Mitsubishi chemical company; PG-100 and CG-500 manufactured by Osaka gas chemical company; "YL 7760" (bisphenol AF-type epoxy resin), "YL 7800" (fluorene-type epoxy resin), "jER 1010" (solid bisphenol A-type epoxy resin), and "jER 1031S" (tetraphenylethane-type epoxy resin) manufactured by Mitsubishi chemical corporation. These may be used alone or in combination of two or more.

When a liquid epoxy resin and a solid epoxy resin are used in combination as the component (D), the amount ratio thereof (liquid epoxy resin: solid epoxy resin) is preferably 1: 0.1-1: 20, more preferably 1: 0.3-1: 15, particularly preferably 1: 1-1: 10. by making the amount ratio of the liquid epoxy resin to the solid epoxy resin within the range, the desired effects of the present invention can be remarkably obtained. Further, when the resin sheet is used in the form of a resin sheet, appropriate adhesion can be obtained. In addition, when the resin sheet is used in the form of a resin sheet, sufficient flexibility is obtained, and handling properties are improved. Further, a cured product having sufficient breaking strength can be usually obtained.

The epoxy equivalent of the epoxy resin as the component (D) is preferably 50 g/eq.about 5000g/eq, more preferably 50 g/eq.about 3000g/eq, still more preferably 80 g/eq.about 2000g/eq, and still more preferably 110 g/eq.about 1000g/eq. When the amount is within this range, a cured product having a sufficient crosslinking density of a cured product of the resin composition can be obtained. The epoxy equivalent is the mass of the epoxy resin containing 1 equivalent of the epoxy group. The epoxy equivalent can be measured according to JIS K7236.

The weight average molecular weight (Mw) of the epoxy resin as the component (D) is preferably 100 to 5000, more preferably 250 to 3000, further preferably 400 to 1500, from the viewpoint of remarkably obtaining the desired effect of the present invention. The weight average molecular weight of the epoxy resin is a weight average molecular weight in terms of polystyrene measured by a Gel Permeation Chromatography (GPC) method.

From the viewpoint of obtaining a cured product exhibiting good mechanical strength and insulation reliability, the content of the epoxy resin as the component (D) is preferably 10 mass% or more, more preferably 15 mass% or more, and further preferably 20 mass% or more, assuming that the nonvolatile component in the resin composition is 100 mass%. From the viewpoint of remarkably obtaining the desired effect of the present invention, the upper limit of the content of the epoxy resin is preferably 40% by mass or less, more preferably 30% by mass or less, particularly preferably 25% by mass or less.

The amount ratio of the epoxy resin as the component (D) to the component (a) is represented by [ the total number of epoxy groups of the epoxy resin ]: the ratio of [ (total number of unsaturated bonds of component (A) ] is preferably 1: 0.01-1: 5, preferably 1: 0.03 to 1: 3, more preferably 1: 0.05-1: 1. here, the "number of epoxy groups of the epoxy resin" refers to a total value of all values obtained by dividing the mass of nonvolatile components of the epoxy resin present in the resin composition by the epoxy equivalent weight. The term "the number of unsaturated bonds in the component (a)" means a total value of all the values obtained by dividing the mass of nonvolatile components of the component (a) present in the resin composition by the equivalent weight of unsaturated bonds. When the amount ratio of the epoxy resin to the component (a) is within the above range, the effect of the present invention can be remarkably obtained.

When the content of the component (A) is represented by a1 assuming that the nonvolatile content of the resin composition is 100% by mass and the content of the epoxy resin as the component (D) assuming that the nonvolatile content of the resin composition is 100% by mass is represented by D1, the D1/a1 ratio is preferably 1 or more, more preferably 3 or more, still more preferably 4 or more, preferably 20 or less, still more preferably 15 or less, and still more preferably 10 or less. By making the adjustment so that d1/a1 is within the range, the effects of the present invention can be obtained remarkably.

As the active ester resin as the component (D), a resin having 1 or more active ester groups in 1 molecule can be used. Among them, as the active ester resin, a resin having 2 or more ester groups having high reactivity in 1 molecule, such as phenol esters, thiophenol esters, N-hydroxylamine esters, and esters of heterocyclic hydroxy compounds, is preferable. The active ester resin is preferably a resin obtained by a condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxyl compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester resin obtained from a carboxylic acid compound and a hydroxyl compound is preferable, and an active ester resin obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferable.

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

Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol a, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol a, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α -naphthol, β -naphthol, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadiene type diphenol compound, and phenol novolac resin. Here, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing 2 molecules of phenol with 1 molecule of dicyclopentadiene.

Preferred specific examples of the active ester resin include an active ester resin having a dicyclopentadiene type diphenol structure, an active ester resin having a naphthalene structure, an active ester resin containing an acetylated product of a phenol novolak resin, and an active ester resin containing a benzoylated product of a phenol novolak resin. Among them, active ester resins having a naphthalene structure and active ester resins having a dicyclopentadiene type diphenol structure are more preferable. "Dicyclopentadiene-type diphenol structure" means a divalent structural unit formed from phenylene-dicyclopentylene (ジシクロペンチレン) -phenylene.

As commercially available active ester resins, for example, the active ester resins containing a dicyclopentadiene type diphenol structure include "EXB 9451", "EXB 9460S", "HPC-8000-65T", "HPC-8000H-65 TM", "EXB-8000L-65 TM" (manufactured by DIC); examples of the active ester-based resin having a naphthalene structure include "EXB 9416-70 BK", "EXB-8100L-65T", "EXB-8150-62T", "HPC-8150-60T", "HPC-8150-62T" (manufactured by DIC); examples of the active ester resin containing an acetylated phenol novolac resin include "DC 808" (manufactured by Mitsubishi chemical corporation); examples of the active ester resin of the benzoyl compound containing a phenol novolac resin include "YLH 1026" (manufactured by mitsubishi chemical corporation); examples of the active ester resin of an acetylated phenol novolac resin include "DC 808" (manufactured by mitsubishi chemical corporation); examples of the active ester resin of the benzoyl compound of the phenol novolac resin include "YLH 1026" (manufactured by mitsubishi chemical corporation), "YLH 1030" (manufactured by mitsubishi chemical corporation), and "YLH 1048" (manufactured by mitsubishi chemical corporation); "EXB-8500-65T" (manufactured by DIC).

The phenol-based resin and the naphthol-based resin as the component (D) are preferably resins having a phenolic (novolac) structure from the viewpoint of heat resistance and water resistance. In addition, from the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenol curing agent is preferred, and a triazine skeleton-containing phenol resin is more preferred.

Specific examples of the phenol-based resin and naphthol-based resin include "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Minghu chemical Co., Ltd; "NHN", "CBN" and "GPH" manufactured by Nippon chemical Co., Ltd.; "SN 170", "SN 180", "SN 190", "SN 475", "SN 485", "SN 495V", "SN 375", "SN 395", manufactured by Nippon iron chemical materials, Inc.; TD-2090, LA-7052, LA-7054, LA-1356, LA-3018-50P and EXB-9500, all available from DIC.

Specific examples of the benzoxazine-based resin as the component (D) include: JBZ-OD100 (benzoxazine ring equivalent of 218), "JBZ-OP 100D (benzoxazine ring equivalent of 218), and" ODA-BOZ "(benzoxazine ring equivalent of 218), manufactured by JFE chemical company; p-d (equivalent of benzoxazine ring is 217) and F-a (equivalent of benzoxazine ring is 217) manufactured by four national chemical industry company; "HFB 2006M" (benzoxazine ring equivalent of 432) manufactured by Showa Polymer Co., Ltd.

Examples of the cyanate ester-based resin as the component (D) include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1, 5-phenylene cyanate), 4 '-methylenebis (2, 6-dimethylphenylene cyanate), 4' -ethylenediphenyl dicyanate, hexafluorobisphenol A dicyanate, difunctional cyanate ester resins such as 2, 2-bis (4-cyanate ester) phenylpropane, 1-bis (4-cyanate ester phenylmethane), bis (4-cyanate ester-3, 5-dimethylphenyl) methane, 1, 3-bis (4-cyanate ester-phenyl-1- (methylethylidene)) benzene, bis (4-cyanate ester-phenyl) sulfide, and bis (4-cyanate ester-phenyl) ether; polyfunctional cyanate ester resins derived from phenol novolac resins, cresol novolac resins, and the like; prepolymers obtained by partially triazinating these cyanate ester resins; and so on. Specific examples of cyanate ester resins include "PT 30", "PT 30S" and "PT 60" (phenol novolac type polyfunctional cyanate ester resin), "ULL-950S" (polyfunctional cyanate ester resin), "BA 230" and "BA 230S 75" (prepolymer obtained by triazinating a part or all of bisphenol a dicyanate ester to form a trimer), which are manufactured by Lonza Japan.

Specific examples of the carbodiimide-based resin as the component (D) include CARBODILITE (registered trademark) V-03 (carbodiimide equivalent: 216), V-05 (carbodiimide equivalent: 216), and V-07 (carbodiimide equivalent: 200) manufactured by Nissin chemical corporation; v-09 (carbodiimide equivalent: 200); stabaxol (registered trademark) P (carbodiimide equivalent: 302) manufactured by Rhein Chemie.

The amine resin as the component (D) includes resins having 1 or more amino groups in the molecule, and examples thereof include aliphatic amines, polyetheramines, alicyclic amines, aromatic amines, and the like, and among them, aromatic amines are preferable from the viewpoint of exhibiting the desired effects of the present invention. The amine-based resin is preferably a primary or secondary amine, more preferably a primary amine. Specific examples of the amine-based resin include 4,4 '-methylenebis (2, 6-dimethylaniline), diphenyldiaminosulfone, 4' -diaminodiphenylmethane, 4 '-diaminodiphenylsulfone, 3' -diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4 '-diaminodiphenyl ether, 3' -dimethyl-4, 4 '-diaminobiphenyl, 2' -dimethyl-4, 4 '-diaminobiphenyl, 3' -dihydroxybenzidine, 2-bis (3-amino-4-hydroxyphenyl) propane, 3-dimethyl-5, 5-diethyl-4, 4-diphenylmethanediamine, and, 2, 2-bis (4-aminophenyl) propane, 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' -bis (4-aminophenoxy) biphenyl, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4- (3-aminophenoxy) phenyl) sulfone and the like. As the amine-based resin, commercially available products can be used, and examples thereof include "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD A-A", "KAYAHARD A-B", "KAYAHARD A-S" manufactured by Nippon chemical company, and "Epicure (エピキュア) W" manufactured by Mitsubishi chemical company.

Examples of the acid anhydride resin as the component (D) include resins having 1 or more acid anhydride groups in 1 molecule. Specific examples of the acid anhydride-based resin include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5- (2, 5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4' -diphenylsulfone tetracarboxylic dianhydride, 1,3,3a,4,5,9 b-hexahydro-5- (tetrahydro-2, 5-dioxo-3-furyl) -naphtho [1,2-C ] furan-1, 3-dione, ethylene glycol bis (trimellitic anhydride ester), styrene-maleic acid resin obtained by copolymerizing styrene with maleic acid, and other polymer-type acid anhydrides.

When the component (D) contains an epoxy resin and a curing agent, the amount ratio of the epoxy resin to the total curing agent is represented by [ the total number of epoxy groups of the epoxy resin ]: [ total number of reactive groups of curing agent ] is preferably 1: 0.01-1: 5, preferably 1: 0.3-1: 3, more preferably 1: 0.5-1: 2. here, the "number of epoxy groups of the epoxy resin" refers to a total value of all values obtained by dividing the mass of nonvolatile components of the epoxy resin present in the resin composition by the epoxy equivalent weight. The "number of active groups of the curing agent" refers to a total value of all the values obtained by dividing the mass of nonvolatile components of the curing agent present in the resin composition by the equivalent weight of the active groups. When the amount ratio of the epoxy resin to the curing agent is within the above range as the component (D), a cured product having excellent flexibility can be obtained.

From the viewpoint of obtaining a cured product excellent in flexibility, the content of the curing agent as the component (D) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, preferably 10% by mass or less, further preferably 5% by mass or less, further preferably 3% by mass or less, relative to 100% by mass of the nonvolatile component in the resin composition.

From the viewpoint of obtaining a cured product excellent in flexibility, the content of the component (D) is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, preferably 35% by mass or less, further preferably 30% by mass or less, further preferably 25% by mass or less, based on 100% by mass of the nonvolatile component in the resin composition.

(E) curing Accelerator

The resin composition may further contain a curing accelerator as the component (E) as an optional component in addition to the above components. By containing the component (E), polymerization by heat can be further promoted.

Examples of the component (E) include epoxy resin curing accelerators such as phosphorus curing accelerators, amine curing accelerators, imidazole curing accelerators, guanidine curing accelerators and metal curing accelerators; a thermal polymerization curing accelerator such as a peroxide curing accelerator. (E) One of the components may be used alone, or two or more of the components may be used in combination.

Examples of the phosphorus-based curing accelerator include triphenylphosphine, a phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like, with triphenylphosphine and tetrabutylphosphonium decanoate being preferred.

Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4, 6-tris (dimethylaminomethyl) phenol, and 1, 8-diazabicyclo [5.4.0] undecene, with 4-dimethylaminopyridine and 1, 8-diazabicyclo [5.4.0] undecene being preferred.

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

As the imidazole-based curing accelerator, commercially available products can be used, and examples thereof include "P200-H50" manufactured by Mitsubishi chemical corporation.

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

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 the organometallic complex include: organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, organic zinc complexes such as zinc (II) acetylacetonate, 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 the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

Examples of the peroxide-based curing accelerator include peroxides such as di-t-butyl peroxide, t-butylcumyl peroxide, t-butylperoxyacetate, α' -di (t-butylperoxy) diisopropylbenzene, t-butylperoxylaurate, t-butylperoxy 2-ethylhexanoate, t-butylperoxyneodecanoate, and t-butylperoxybenzoate.

Examples of commercially available peroxide-based curing accelerators include "PERHEXYL D", "PERBUTYL C", "PERBUTYL A", "PERBUTYL P", "PERBUTYL L", "PERBUTYL O", "PERBUTYL ND", "PERBUTYL Z", "PERCUYL P" and "PERCUPYL D", manufactured by Nissan oil Co., Ltd.

From the viewpoint of remarkably obtaining the desired effect of the present invention, the content of the component (E) is preferably 0.1 mass% or more, more preferably 0.2 mass% or more, further preferably 0.3 mass% or more, further preferably 1 mass% or less, further preferably 0.8 mass% or less, further preferably 0.5 mass% or less, with respect to 100 mass% of nonvolatile components in the resin composition.

< (F) other additives

The resin composition may further contain other additives as optional components in addition to the above components. Examples of such additives include: (B) other components, thermoplastic resin, thickening agent, defoaming agent, leveling agent, adhesion imparting agent and other resin additives. These additives may be used singly or in combination of two or more. The respective contents may be appropriately set by those skilled in the art.

The method for producing the resin composition of the present invention is not particularly limited, and examples thereof include: a method of adding the compounding ingredients, adding a solvent or the like as needed, and mixing and dispersing the mixture by using a rotary mixer or the like.

< Properties and uses of resin composition >

The resin composition contains the component (A) and a predetermined amount of the component (B). This can suppress the cure shrinkage and can provide a cured product having an excellent dielectric constant. In addition, a cured product having an excellent dielectric loss tangent can be obtained.

A cured product obtained by thermally curing the resin composition at 190 ℃ for 90 minutes exhibits a low cure shrinkage. That is, curing shrinkage can be suppressed, thereby providing an insulating layer in which warpage can be suppressed. The curing shrinkage is preferably 0.35% or less, more preferably 0.34% or less, and still more preferably 0.33% or less. The lower limit of the curing shrinkage is not particularly limited, and may be 0.01% or more. The curing shrinkage can be measured by the method described in the following examples.

A cured product obtained by thermally curing the resin composition at 190 ℃ for 90 minutes exhibits a low dielectric constant. Therefore, the cured product provides an insulating layer having a low dielectric constant. The dielectric constant is preferably 3.0 or less, more preferably 2.9 or less, further preferably 2.85 or less. The lower limit of the dielectric constant may be 0.001 or more. The dielectric constant can be measured by the method described in the following examples.

A cured product obtained by thermally curing the resin composition at 190 ℃ for 90 minutes exhibits a low dielectric loss tangent. Therefore, the cured product provides an insulating layer having a low dielectric loss tangent. The dielectric loss tangent is preferably 0.01 or less, more preferably 0.007 or less, still more preferably 0.005 or less. The lower limit value of the dielectric loss tangent may be 0.0001 or higher. The dielectric loss tangent can be measured by the method described in the following examples.

The resin composition of the present invention can suppress the curing shrinkage and can provide an insulating layer having an excellent dielectric constant. Therefore, the resin composition of the present invention can be suitably used as a resin composition for insulation applications. Specifically, it can be suitably used as: a resin composition for forming an insulating layer (a 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.

In addition, in the following multilayer printed wiring board, it can be suitably used: the resin composition for forming an insulating layer of a multilayer printed wiring board (resin composition for forming an insulating layer of a multilayer printed wiring board), the resin composition for forming an interlayer insulating layer of a printed wiring board (resin composition for forming an interlayer insulating layer of a printed wiring board), and the resin composition for forming an insulating layer of a flexible substrate (resin composition for forming an insulating layer of a flexible substrate).

In addition, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention can be suitably used as: a resin composition for a rewiring-forming layer (a resin composition for forming a rewiring-forming layer) as an insulating layer for forming a rewiring layer; and a resin composition for sealing a semiconductor chip (resin composition for sealing a semiconductor chip). At the time of manufacturing the semiconductor chip package, a rewiring layer may be further formed on the sealing layer;

(1) a step of laminating a temporary fixing film on the substrate,

(2) A step of temporarily fixing the semiconductor chip to the temporary fixing film,

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

(4) A step of peeling the base material and the temporary fixing film from the semiconductor chip,

(5) A step of forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film are peeled, and

(6) and forming a rewiring layer as a conductor layer on the rewiring-forming layer.

[ resin sheet ]

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

From the viewpoint of thinning of the printed wiring board and providing a cured product excellent in insulation even when the cured product of the resin composition is a thin film, the thickness of the resin composition layer is preferably 50 μm or less, more preferably 40 μm or less, and further preferably 30 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, and may be usually 5 μm or more.

Examples of the support include a film made of a plastic material, a metal foil, and a release paper, and a film made of a plastic material and a metal foil are preferable.

When a film made of a plastic material is used as the support, examples of the plastic material include: polyester such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"), acrylic polymer such as polycarbonate (hereinafter sometimes abbreviated as "PC") and polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, and the like. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and particularly, inexpensive polyethylene terephthalate is preferable.

When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil, and copper foil is preferred. As the copper foil, a foil formed of a single metal of copper may be used, and a foil formed of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, or the like) may also be used.

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

In addition, as the support, a support with a release layer having a release layer on the surface bonded to the resin composition layer can be used. Examples of the release agent used for the release layer of the support with a release layer include 1 or more release agents selected from alkyd resins, polyolefin resins, polyurethane resins, and silicone resins. As the support with a release layer, commercially available products can be used, and examples thereof include: examples of the PET film having a release layer containing an alkyd resin-based release agent as a main component include "SK-1", "AL-5" and "AL-7" manufactured by Lindcaceae, "LUMIRROR T60" manufactured by Toray, "Purex" manufactured by Ditikon, and "Unipel" manufactured by Unitika.

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

In one embodiment, the resin sheet may further contain other layers as necessary. Examples of such other layers include a protective film for the support provided on the surface of the resin composition layer not bonded to the support (i.e., the surface opposite to the support). The thickness of the protective film is not particularly limited, and is, for example, 1 μm to 40 μm. By laminating the protective film, adhesion of dust or the like to the surface of the resin composition layer and formation of scratches can be suppressed.

The resin sheet can be produced, for example, by: a resin varnish obtained by dissolving a resin composition in an organic solvent is prepared, and the resin varnish is applied to a support by a die coater (die coater) or the like, and further dried to form a resin composition layer.

Examples of the organic solvent include ketones such as acetone, Methyl Ethyl Ketone (MEK), and cyclohexanone; acetates such as ethyl acetate, butyl acetate, cellosolve acetate (cellosolve acetate), propylene glycol monomethyl ether acetate and carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. One kind of the organic solvent may be used alone, or two or more kinds may be used in combination.

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

The resin sheet can be stored in a roll form. When the resin sheet has a protective film, the protective film can be peeled off and used.

[ printed Wiring Board ]

The printed wiring board of the present invention includes an insulating layer formed using a cured product of the resin composition of the present invention.

The printed wiring board can be produced, for example, by a method including the following steps (I) and (II) using the above-described resin sheet:

(I) laminating the resin sheet on the inner substrate so that the resin composition layer of the resin sheet is bonded to the inner substrate;

(II) a step of forming an insulating layer by thermally curing the resin composition layer.

The "inner layer substrate" used in the step (I) is a member to be a substrate of a printed wiring board, and examples thereof include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like. In addition, the substrate may have a conductive layer on one or both surfaces thereof, and the conductive layer may be subjected to patterning. An inner layer substrate having a conductor layer (circuit) formed on one surface or both surfaces of a substrate is sometimes referred to as an "inner layer circuit substrate". In addition, an intermediate product in which an insulating layer and/or a conductor layer is to be further formed when manufacturing a printed wiring board is also included in the "inner layer substrate" in the present invention. When the printed wiring board is a component-embedded circuit board, an inner layer substrate in which components are embedded may be used.

The lamination of the inner layer substrate and the resin sheet can be performed, for example, by heat-pressure bonding the resin sheet to the inner layer substrate from the support side. Examples of the member for heat-pressure bonding the resin sheet to the inner substrate (hereinafter also referred to as "heat-pressure bonding member") include a heated metal plate (SUS end plate (or other plate)) and a metal roll (SUS roll). It is preferable that the heating and pressure-bonding member is not directly pressed against the resin sheet, but is pressed through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the inner layer substrate.

The lamination of the inner substrate and the resin sheet may be performed by a vacuum lamination method. In the vacuum lamination method, the heating and press-bonding temperature is preferably in the range of 60 to 160 ℃, more preferably 80 to 140 ℃, the heating and press-bonding pressure is preferably in the range of 0.098 to 1.77MPa, more preferably 0.29 to 1.47MPa, and the heating and press-bonding time is preferably in the range of 20 to 400 seconds, more preferably 30 to 300 seconds. The lamination is preferably carried out under a reduced pressure of 26.7hPa or less.

The lamination may be performed by a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressure laminator manufactured by Nikko-Materials, a vacuum applicator manufactured by Nikko-Materials, and a batch vacuum pressure laminator.

The smoothing treatment of the laminated resin sheets may be performed after lamination, for example, by pressing the heat crimping member from the support side under normal pressure (atmospheric pressure). The pressing conditions for the smoothing treatment may be the same as the above-described conditions for the heat and pressure bonding of the laminate. The smoothing treatment may be performed by a commercially available laminator. The lamination and smoothing treatment can be continuously performed using a commercially available vacuum laminator as described above.

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

In the step (II), the resin composition layer is thermally cured to form the insulating layer. The conditions for heat curing of the resin composition layer are not particularly limited, and the conditions generally used in forming an insulating layer of a printed wiring board can be used.

For example, the heat curing conditions of the resin composition layer vary depending on the kind of the resin composition, and the curing temperature is preferably 120 to 240 ℃, more preferably 150 to 220 ℃, and further preferably 170 to 210 ℃. The curing time is preferably from 5 minutes to 120 minutes, more preferably from 10 minutes to 100 minutes, further preferably from 15 minutes to 100 minutes.

The resin composition layer may be preheated at a temperature lower than the curing temperature before the resin composition layer is thermally cured. For example, the resin composition layer may be preheated for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, further preferably 15 minutes to 100 minutes) at a temperature of 50 ℃ or more and less than 120 ℃ (preferably 60 ℃ or more and 115 ℃ or less, further preferably 70 ℃ or more and 110 ℃ or less) before the resin composition layer is thermally cured.

In the production of the printed wiring board, (III) a step of forming a hole in the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer may be further performed. These steps (III) to (V) may be carried out by various methods known to those skilled in the art used in the production of printed wiring boards. When the support is removed after step (II), the support may be removed between step (II) and step (III), between step (III) and step (IV), or between step (IV) and step (V). If necessary, the insulating layer and the conductive layer in steps (II) to (V) may be repeatedly formed to form a multilayer wiring board.

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

The step (IV) is a step of roughening the insulating layer. In general, in this step (IV), the removal of the scum is also performed. The roughening treatment step and conditions are not particularly limited, and known steps and conditions generally used for forming an insulating layer of a printed wiring board can be used. For example, the insulating layer may be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralizing treatment with a neutralizing liquid in this order. The swelling liquid used for the roughening treatment is not particularly limited, and examples thereof include an alkali solution, a surfactant solution and the like, preferably an alkali solution, and more preferably a sodium hydroxide solution and a potassium hydroxide solution. Examples of commercially available Swelling liquids include "spinning Dip securigant P", "spinning Dip securigant SBU" and "spinning Dip securigant P" manufactured by atmet JAPAN (ato ech JAPAN). The swelling treatment with the swelling solution is not particularly limited, and for example, the insulating layer can be immersed in the swelling solution at 30 to 90 ℃ for 1 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 solution at 40 to 80 ℃ for 5 to 15 minutes. The oxidizing agent used in the roughening treatment is not particularly limited, and examples thereof include an alkaline permanganic acid solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. 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 to 100 ℃ for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5 to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as "Concentrate Compact CP" and "Dosing solution securiganteh P" manufactured by amett japan. The neutralizing solution used for the roughening treatment is preferably an acidic aqueous solution, and examples of commercially available products include "Reduction solution securiganteh P" manufactured by amatt japan. The treatment with the neutralizing solution can be performed by immersing the treated surface subjected to the roughening treatment with the oxidizing agent in the neutralizing solution at 30 to 80 ℃ for 1 to 30 minutes. From the viewpoint of handling and the like, it is preferable to dip the object subjected to the roughening treatment with the oxidizing agent in a neutralizing solution at 40 to 70 ℃ for 5 to 20 minutes.

In one embodiment, the arithmetic average roughness (Ra) of the surface of the insulating layer after the roughening treatment is preferably 300nm or less, more preferably 250nm or less, and still more preferably 200nm or less. The lower limit is not particularly limited, but is preferably 30nm or more, more preferably 40nm or more, and still more preferably 50nm or more. The arithmetic average roughness (Ra) 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 for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer contains 1 or more metals selected from gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductor layer may be a single metal layer or an alloy layer, and examples of the alloy layer include layers formed of an alloy of 2 or more metals selected from the above metals (e.g., a nickel-chromium alloy, a copper-nickel alloy, and a copper-titanium alloy). Among them, from the viewpoint of versatility of forming a conductor layer, cost, ease of patterning, and the like, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of a nickel-chromium alloy, a copper-nickel alloy, or a copper-titanium alloy is preferable, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of a nickel-chromium alloy is more preferable, and a single metal layer of copper is even more preferable.

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

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

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

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern for exposing a part of the plating seed layer is formed on the formed plating seed layer in accordance with a desired wiring pattern. After a metal layer is formed on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. Then, the unnecessary plating seed layer is removed by etching or the like, whereby a conductor layer having a desired wiring pattern can be formed.

[ multilayer Flexible substrate ]

The multilayer flexible substrate includes an insulating layer formed using a cured product of the resin composition of the present invention. The multilayer flexible substrate may include any member combined with an insulating layer. Examples of the optional member include an electronic component and a cover film.

The multilayer flexible substrate can be manufactured by a manufacturing method including a method of manufacturing a laminated sheet manufactured by laminating and curing a plurality of resin composition layers. Accordingly, the multilayer flexible substrate can be manufactured by a manufacturing method including the steps of: (a) a step of preparing a resin sheet, and (b) a step of laminating and curing a plurality of resin composition layers using the resin sheet.

The method for manufacturing a multilayer flexible substrate may further include any process combined with the above-described process. For example, a method for manufacturing a multilayer flexible substrate including an electronic component may include a step of bonding the electronic component to the laminated sheet. As for the bonding condition between the laminated sheet and the electronic component, any condition can be adopted in which the terminal electrode of the electronic component and the conductor layer provided on the laminated sheet as a wiring can be conductor-connected. For example, the method for manufacturing a multilayer flexible substrate provided with a cover film may include a step of laminating a laminated sheet and the cover film.

A multilayer flexible substrate can be generally used by bending a laminated sheet included in the multilayer flexible substrate so that one surface faces each other. For example, the multilayer flexible substrate is housed in a case of a semiconductor device in a state of being bent and reduced in size. In addition, for example, in a semiconductor device having a flexible movable portion, a multilayer flexible substrate is provided in the movable portion.

[ semiconductor device ]

The semiconductor device of the present invention includes the printed wiring board or the multilayer flexible substrate of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring board or the multilayer flexible substrate of the present invention.

Examples of the semiconductor device include various semiconductor devices used in electric products (for example, a computer, a mobile phone, a digital camera, a television, and the like) and vehicles (for example, a motorcycle, an automobile, a train, a ship, an aircraft, and the like).

The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) at a conducting position of a printed wiring board. The "conduction position" refers to a "position of the printed wiring board where an electrical signal is conducted", and the position may be either a surface or a buried position. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

A method of mounting a semiconductor chip in the manufacture of a semiconductor device is not particularly limited as long as the semiconductor chip can function effectively, and specific examples thereof include a wire bonding mounting method, a flip chip mounting method, a mounting method by a build-up layer without solder (BBUL), a mounting method by an Anisotropic Conductive Film (ACF), a mounting method by a nonconductive film (NCF), and the like. The "mounting method by a build-up solderless layer (BBUL)" referred to herein is a "mounting method in which a semiconductor chip is directly embedded in a recess of a printed wiring board and the semiconductor chip is connected to a wiring on the printed wiring board".

Examples

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the following description, "part" and "%" mean "part by mass" and "% by mass", respectively, unless otherwise stated.

< Synthesis example 1: synthesis of polyimide resin 1

A500 ml separable flask equipped with a nitrogen inlet tube and a stirrer was charged with 9.13g (30 mmol) of 5-amino-1, 1' -biphenyl-2-yl 4-aminobenzoate (compound of formula (B-3)), 15.61g (30 mmol) of 4,4' - (4,4' -isopropylidenediphenoxy) diphthalic dianhydride, 94.64g of N-methyl-2-pyrrolidone, 0.47g (6 mmol) of pyridine, and 10g of toluene, and imidization was performed for 4 hours at 180 ℃ while toluene was discharged out of the system, thereby obtaining a polyimide solution (nonvolatile content: 20 mass%) containing polyimide resin 1. In the polyimide solution, no precipitation of the synthesized polyimide resin 1 was observed. The weight average molecular weight of the polyimide resin 1 was 45000.

< Synthesis example 2: synthesis of polyimide resin 2

A reaction vessel equipped with a stirrer, a water separator, a thermometer, and a nitrogen gas inlet was charged with 65.0g of aromatic tetracarboxylic dianhydride (BisDA-1000 manufactured by SABIC Japan; 4,4'- (4,4' -isopropylidenediphenoxy) diphthalic dianhydride), 266.5g of cyclohexanone, and 44.4g of methylcyclohexane, and the solution was heated to 60 ℃. Then, 43.7g of dimer diamine ("PRIAMINE 1075" manufactured by Croda Japan) and 5.4g of 1, 3-bis (aminomethyl) cyclohexane were added dropwise thereto, and imidization was carried out at 140 ℃ for 1 hour. Thus, a polyimide solution (nonvolatile content: 30% by mass) containing the polyimide resin 2 was obtained. Further, the weight average molecular weight of the polyimide resin 2 was 25000.

< Synthesis example 3: synthesis of polyimide resin 3

A500 mL separable flask equipped with a quantitative moisture receiver connected to a reflux condenser, a nitrogen inlet tube, and a stirrer was prepared. In the flask, 20.3g of 4,4' -oxydiphthalic anhydride (ODPA), 200g of gamma-butyrolactone, 20g of toluene, and 29.6g of 5- (4-aminophenoxy) -3- [4- (4-aminophenoxy) phenyl ] -1,1, 3-trimethylindane were charged, and the mixture was stirred at 45 ℃ for 2 hours under a nitrogen stream to effect a reaction. Subsequently, the reaction solution was heated to about 160 ℃ and, while maintaining the temperature, the condensation water was azeotropically removed together with toluene under a nitrogen stream. The results of "a predetermined amount of water was stored in the quantitative water receiver" and "no outflow of water was observed" were confirmed. After confirmation, the reaction solution was further heated and stirred at 200 ℃ for 1 hour. Then, the mixture was cooled to obtain a polyimide solution (nonvolatile content: 20 mass%) containing a polyimide resin 3 having a1, 1, 3-trimethylindan skeleton. The polyimide resin 3 thus obtained has a repeating unit represented by the following formula (X1) and a repeating unit represented by the following formula (X2). The weight average molecular weight of the polyimide resin 3 was 12000.

[ chemical formula 15]

[ chemical formula 16]

< Synthesis example 4: synthesis of Compound A having an aromatic ester skeleton and an unsaturated bond (Compound A) >

89 parts by mass of o-allylphenol, 110 parts by mass of dicyclopentadiene-phenol copolymer resin (softening point 85 ℃ C., hydroxyl equivalent of about 165g/eq.) and 1000 parts by mass of toluene were charged into a reaction vessel, and the components were dissolved while replacing the inside of the vessel with nitrogen under reduced pressure. Subsequently, 135 parts by mass of isophthaloyl dichloride was charged and dissolved. Subsequently, 0.5g of tetrabutylammonium bromide was added, and 309g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours while purging the inside of the vessel with nitrogen gas. At this time, the temperature in the system was controlled to 60 ℃ or lower. Then, the reaction was stirred for 1 hour. After the reaction was completed, the reaction mixture was separated and the aqueous layer was removed. This operation was repeated until the pH of the aqueous layer became 7, and toluene or the like was distilled off under heating and reduced pressure to obtain compound A having an aromatic ester skeleton and an unsaturated bond. The equivalent weight of unsaturated bonds in the obtained compound A having an aromatic ester skeleton and unsaturated bonds was 428g/eq, when calculated from the charge ratio. The compound A is represented by the following formula, s represents an integer of 0 or 1 or more, and the average value of r calculated from the charge ratio is 1. The wavy line has a structure obtained by reacting isophthaloyl dichloride with a phenol polyaddition reaction resin and/or o-allylphenol;

[ chemical formula 17]

< Synthesis example 5: synthesis of Compound B having an aromatic ester skeleton and an unsaturated bond (Compound B) >

A reaction vessel was charged with 201 parts by mass of o-allylphenol and 1000 parts by mass of toluene, and the above components were dissolved while the inside of the vessel was purged with nitrogen under reduced pressure. Subsequently, 152 parts by mass of isophthaloyl dichloride was charged and dissolved. 309g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours while purging the inside of the vessel with nitrogen gas. At this time, the temperature in the system was controlled to 60 ℃ or lower. Then, the reaction was stirred for 1 hour. After the reaction was completed, the reaction mixture was separated and the aqueous layer was removed. This operation was repeated until the pH of the aqueous layer became 7, and toluene or the like was distilled off under heating and reduced pressure to obtain compound B containing an aromatic ester skeleton and an unsaturated bond. The equivalent weight of unsaturated bonds in the obtained compound B having an aromatic ester skeleton and unsaturated bonds was 199g/eq when calculated from the charge ratio. Compound B is a structure represented by the following formula;

[ chemical formula 18]

< example 1: preparation of resin composition 1

While stirring, 5 parts of a bicresol-type epoxy resin ("YX 4000 HK" manufactured by mitsubishi chemical corporation, having an epoxy equivalent of about 185g/eq.)5 parts, a naphthalene-type epoxy resin ("ESN 475V" manufactured by shin-kunjin chemical corporation, having an epoxy equivalent of about 332g/eq.)5 parts, a bisphenol AF-type epoxy resin ("YL 7760" manufactured by mitsubishi chemical corporation, having an epoxy equivalent of about 238g/eq.)10 parts, and a cyclohexane-type epoxy resin ("ZX 1658 GS" manufactured by mitsubishi chemical corporation, having an epoxy equivalent of about 135g/eq.)2 parts were heated and dissolved in a mixed solvent of 100 parts of the polyimide resin 1 (20% by mass of nonvolatile content) and 10 parts of cyclohexanone obtained in synthetic example 1. Is cooled to5 parts of the compound A obtained in Synthesis example 4,4 parts of a triazine skeleton-containing cresol novolak-based curing agent ("LA 3018-50P" manufactured by DIC corporation, 2-methoxypropanol solution having a hydroxyl group equivalent of about 151g/eq. and a solid content of 50%), and spherical silica ("SC 2500 SQ" manufactured by Yadu Ma corporation, having an average particle diameter of 0.5 μm and a specific surface area of 11.2m were mixed at room temperature²Per g, 100 parts of silica was surface-treated with 50 parts of N-phenyl-3-aminopropyltrimethoxysilane (KBM 573, manufactured by shin-Etsu chemical Co., Ltd.), 0.2 part of an amine-based curing accelerator (4-Dimethylaminopyridine (DMAP)) and 0.03 part of a peroxide-based curing accelerator ("PERBUTYL C", manufactured by Nikkiso Co., Ltd.) and uniformly dispersed in a high-speed rotary mixer, and then filtered through a drum filter ("SHP 020", manufactured by ROKITECHNNO Co., Ltd.) to prepare a resin composition 1.

< example 2: preparation of resin composition 2

In example 1,5 parts of compound a was changed to 10 parts of compound B (nonvolatile content 50 mass%). In the same manner as in example 1 except for the above, resin composition 2 was prepared.

< example 3: preparation of resin composition 3

In example 1, 100 parts of the polyimide resin 1 (nonvolatile component 20 mass%) obtained in synthesis example 1 was changed to 66.7 parts of the polyimide resin 2 (nonvolatile component 30 mass%) obtained in synthesis example 2. In the same manner as in example 1 except for the above matters, resin composition 3 was prepared.

< example 4: preparation of resin composition 4

In example 1, 100 parts of the polyimide resin 1 (nonvolatile component 20 mass%) obtained in synthesis example 1 was changed to 100 parts of the polyimide resin 3 (nonvolatile component 20 mass%) obtained in synthesis example 3. In the same manner as in example 1 except for the above matters, a resin composition 4 was prepared.

< comparative example 1: preparation of resin composition 5

In example 1,5 parts of the compound A obtained in Synthesis example 4 was changed to 7.7 parts of an active ester-based curing agent (EXB-8000L-65 TM, manufactured by DIC corporation, active group equivalent: about 220g/eq., toluene having 65% by mass of nonvolatile content: 1 solution of MEK). In the same manner as in example 1 except for the above matters, resin composition 5 was prepared.

Comparative example 2: preparation of resin composition 6

In example 1,5 parts of the compound A obtained in Synthesis example 4 was changed to 8.1 parts of an active ester-based curing agent ("EXB-8150-62T" manufactured by DIC corporation, having an active group equivalent of about 230g/eq., and a toluene solution containing 62% by mass of nonvolatile matter). In the same manner as in example 1 except for the above matters, resin composition 6 was prepared.

< measurement of average particle diameter of inorganic Filler >

100mg of the inorganic filler and 10g of methyl ethyl ketone were weighed into a vial, and dispersed by ultrasonic waves for 10 minutes. The particle size distribution of the inorganic filler was measured on a volume basis by a flow cell (flowcell) system using a laser diffraction type particle size distribution measuring apparatus ("LA-960" manufactured by horiba ltd.) with the wavelengths of the light source used being blue and red. The average particle diameter of the inorganic filler was calculated from the obtained particle diameter distribution as a median particle diameter.

< determination of specific surface area of inorganic Filler >

The specific surface area of the inorganic filler was measured by adsorbing nitrogen gas onto the surface of the sample using a BET full-automatic specific surface area measuring apparatus (Macsorb HM-1210, MOUNTECH Co., Ltd.) and calculating the specific surface area using the BET multipoint method.

< measurement of curing shrinkage >

(1-1) preparation of resin sheet

The resin compositions of examples and comparative examples were uniformly applied to the release-treated surface of a PET film (thickness: 38 μm) treated with an alkyd resin-based release agent using a die coater so that the thickness of the dried resin composition layer became 40 μm, and dried at 80 to 120 ℃ (average 100 ℃) for 6 minutes, to obtain a resin sheet 1.

(1-2) preparation of polyimide film with resin

After processing the resin sheet 1 into a 200mm square, the resin composition layer was laminated on one surface so that the resin composition layer was in contact with the center of the smooth surface of a polyimide film (UPILEX 25S, 25 μm thick, 240mm square, manufactured by yuken corporation) using a batch vacuum press Laminator (2-Stage build up Laminator, CVP700, manufactured by nichogo-Morton corporation) to obtain a resin-attached polyimide film. Lamination was carried out by: the pressure was reduced for 30 seconds to a pressure of 13hPa or less, and then the resultant was pressure-bonded at 100 ℃ under a pressure of 0.74MPa for 30 seconds.

(1-3) measurement of initial Length

The obtained polyimide film with resin was punched out from the support of the resin sheet to form 4 through-holes (diameter: about 6mm) at a position of about 20mm from the four corners of a square resin having a side length of 200mm (the holes were referred to as A, B, C, D temporarily in the clockwise direction), and after the support of the resin sheet was peeled off, the length L (L) between the centers of the formed holes was measured by a non-contact type image measuring instrument (manufactured by Mitutoyo Co., Quick Vision model: QVH1X606-PRO III _ BHU2G)_AB、L_BC、L_CD、L_DA、L_AC、L_BD) (refer to fig. 1). In fig. 1, X, Y denotes the longitudinal direction and the transverse direction of the resin sheet.

(1-4) Heat curing of resin composition layer

The polyimide film surface of the resin-attached polyimide film after the completion of the measurement was placed on a glass cloth-based epoxy resin double-sided copper-clad laminate (0.7mm thick, "R5715 ES" manufactured by sons electric corporation) having dimensions of 255mm × 255mm, the four sides thereof were fixed with a polyimide tape (width 10mm), and the resin composition layer was heated at 190 ℃ for 90 minutes to obtain a cured product layer by heat curing.

(1-5) measurement of Heat curing shrinkage

After the thermosetting, the polyimide tape was peeled off, the polyimide film with the cured product layer was detached from the laminate, the cured product layer was further peeled off from the polyimide film, and the length L '(L'_AB、L'_BC、L'_CD、L'_DA、L'_AC、L'_BD)。

The length L between the holes A and B is determined by the following formula (1)_ABShrinkage after curing s1_AB. Similarly, L is obtained_BC、L_CD、L_DA、L_ACAnd L_BDShrinkage after curing s1_BC、s1_CD、s1_DA、s1_ACAnd s1_DA；

s1_AB＝(L_AB-L'_AB)/L_AB (1)。

The curing shrinkage of the cured product layer was determined by the following formula (2);

curing shrinkage [ shrinkage in x-y direction: s1 (%)

＝{(s1_AB+s1_BC+s1_CD+s1_DA+s1_AC+s1_DA)/6}×100 (2)。

The curing shrinkage of the cured product layer was evaluated according to the following criteria,

o: the curing shrinkage is less than 0.35%;

x: the curing shrinkage rate exceeds 0.35 percent.

< measurement of dielectric characteristics (dielectric constant, dielectric loss tangent) >

The resin sheet 1 prepared in (1-1) was laminated on a laminate (an etchout copper foil-etched product of MCL-E-700G, manufactured by Hitachi chemical Co., Ltd.) using a batch vacuum pressure laminator ("MVLP-500" manufactured by "Co., Ltd.). For lamination, the pressure was reduced for 30 seconds to 13hPa or less, and then pressure-bonded at 120 ℃ for 30 seconds at a pressure of 0.74 MPa. Then, the PET film was peeled off, and the resin composition layer was cured at 190 ℃ for 90 minutes to obtain a cured product sample.

The sample of the cured product was cut into test pieces having a width of 2mm and a length of 80 mm. For the test piece, the dielectric constant and the dielectric loss tangent were measured by the resonance cavity perturbation method at a measurement frequency of 5.8GHz and a measurement temperature of 23 ℃ using "HP 8362B" manufactured by Agilent technologies. The measurement was performed for 3 test pieces, and the average value was calculated. The dielectric constant was evaluated according to the following criteria,

o: a dielectric constant of 3.0 or less;

x: the dielectric constant exceeds 3.0.

[ Table 1]

In the table, the number of the main points of the drawing,

"(content of component (A)" means the content of component (A) assuming that the nonvolatile content in the resin composition is 100% by mass,

"(B) component content" means the content of the (B) component assuming that the nonvolatile content in the resin composition is 100% by mass,

"the content of the component (C)" represents the content of the component (C) assuming that the nonvolatile content in the resin composition is 100 mass%.

It was confirmed that, in examples 1 to 4, even when the components (C) to (E) were not contained, the results were similar to those in the above examples, although the differences were different in degree.

Claims

1. A resin composition comprising the following components (A) and (B),

(A) a compound having an aromatic ester skeleton and an unsaturated bond,

(B) A polyimide resin,

wherein the content of the component (B) is 10 to 50% by mass, based on 100% by mass of nonvolatile components in the resin composition.

2. The resin composition according to claim 1, wherein the component (A) is any of a compound represented by the following general formula (A-1) and a compound represented by the following general formula (A-2),

in the general formula (A-1),

Ar¹¹each independently represents a monovalent aromatic hydrocarbon group optionally having a substituent,

Ar¹²each independently represents a divalent aromatic hydrocarbon group optionally having a substituent,

Ar¹³each independently represents a divalent aromatic hydrocarbon group optionally having a substituent, a divalent aliphatic hydrocarbon group optionally having a substituent, an oxygen atom, a sulfur atom, or a divalent group formed by combining these groups,

n represents an integer of 0 to 10,

in the general formula (A-2),

Ar²¹represents an m-valent aromatic hydrocarbon group which may have a substituent,

Ar²²each independently represents a monovalent aromatic hydrocarbon group optionally having a substituent,

m represents an integer of 2 or 3.

3. The resin composition according to claim 1, wherein the content of the component (A) is 0.1% by mass or more and 30% by mass or less, assuming that the nonvolatile content in the resin composition is 100% by mass.

4. The resin composition according to claim 1, further comprising (C) an inorganic filler.

5. The resin composition according to claim 4, wherein the content of the component (C) is 30% by mass or more, assuming that the nonvolatile content in the resin composition is 100% by mass.

6. The resin composition according to claim 1, further comprising (D) a thermosetting resin.

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

8. The resin composition according to claim 1, which is used for forming an insulating layer, the insulating layer being an insulating layer for forming a conductor layer.

9. A resin sheet, comprising:

support body, and

a resin composition layer comprising the resin composition according to any one of claims 1 to 8 provided on the support.

10. A printed wiring board comprising an insulating layer formed from a cured product of the resin composition according to any one of claims 1 to 8.

11. A multilayer flexible substrate comprising an insulating layer formed from a cured product of the resin composition according to any one of claims 1 to 8.

12. A semiconductor device comprising the printed wiring board of claim 10.

13. A semiconductor device comprising the multilayer flexible substrate of claim 11.