TWI883019B - Resin composition - Google Patents

Abstract

The subject of the present invention is to provide a resin composition capable of obtaining a cured product having a suppressed curing shrinkage and excellent dielectric constant, a resin sheet containing the resin composition, a printed wiring board having an insulating layer formed using the resin composition, a multilayer flexible substrate, and a semiconductor device. The present invention is a resin composition containing (A) a compound containing an aromatic ester skeleton and an unsaturated bond and (B) a polyimide resin, wherein, when the non-volatile component in the resin composition is 100% by mass, the content of the component (B) is 10% by mass or more and 50% by mass or less.

Description

Resin composition

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

In the manufacturing technology of printed wiring boards, there is a known manufacturing method in which an insulating layer and a conductive layer are assembled by alternately stacking them.

As insulating materials for printed wiring boards having such insulating layers, for example, a resin composition is disclosed in Patent Document 1. [Prior Art Document] [Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2019-6869

[Invention’s Instructions] [Problems that the invention aims to solve]

In recent years, the dielectric constant of the insulating layer has been required to be further improved. In addition, with the popularization of smart phones, the demand for thinner devices has become stronger, so the insulating layer needs to be thinner. If the insulating layer becomes thinner, it tends to warp, so it is required to suppress the curing shrinkage rate of the insulating layer.

The subject of the present invention is a resin composition capable of obtaining a cured product having a suppressed curing shrinkage rate and excellent dielectric constant, a resin sheet containing the resin composition, a printed wiring board and a semiconductor device having an insulating layer formed using the resin composition. [Means for Solving the Problem]

The inventors of the present invention have devoted themselves to studying and examining the above-mentioned problems and have found that the above-mentioned problems can be solved by making the resin composition contain (A) a compound containing an aromatic ester skeleton and an unsaturated bond and a predetermined amount of (B) a polyimide resin.

That is, the present invention includes the following contents. [1] A resin composition comprising (A) a compound containing an aromatic ester skeleton and an unsaturated bond and (B) a polyimide resin, wherein the content of component (B) is from 10% to 50% by mass when the non-volatile components in the resin composition are 100% by mass. [2] A resin composition as described in [1], wherein component (A) is any one of a compound represented by the following general formula (A-1) and a compound represented by the following general formula (A-2). (In general formula (A-1), Ar ¹¹ each independently represents a monovalent aromatic hydrocarbon group which may have a substituent, Ar ¹² each independently represents a divalent aromatic hydrocarbon group which may have a substituent, and Ar ¹³ each independently represents a divalent aromatic hydrocarbon group which may have a substituent, a divalent aliphatic hydrocarbon group which may have a substituent, an oxygen atom, a sulfur atom, or a divalent group composed of a combination thereof. n represents an integer of 0 to 10.) (In general formula (A-2), Ar ²¹ represents an m-valent aromatic hydrocarbon group which may have a substituent, and Ar ²² each independently represents a monovalent aromatic hydrocarbon group which may have a substituent. m represents an integer of 2 or 3.) [3] A resin composition as described in [1] or [2], wherein the content of component (A) is from 0.1 mass % to 30 mass % when the non-volatile components in the resin composition are taken as 100 mass %. [4] A resin composition as described in any one of [1] to [3], further comprising (C) an inorganic filler. [5] A resin composition as described in [4], wherein the content of component (C) is from 30 mass % to 30 mass % when the non-volatile components in the resin composition are taken as 100 mass %. [6] A resin composition as described in any one of [1] to [5], further comprising (D) a thermosetting resin. [7] A resin composition as described in any one of [1] to [6], which is used for forming an insulating layer. [8] A resin composition as described in any one of [1] to [7], which is used for forming an insulating layer for forming a conductive layer. [9] A resin sheet comprising a support and a resin composition layer comprising the resin composition as described in any one of [1] to [8] disposed on the support. [10] A printed wiring board comprising an insulating layer formed by a cured product of the resin composition as described in any one of [1] to [8]. [11] A multi-layer flexible substrate comprising an insulating layer formed by a cured product of the resin composition of any one of [1] to [8]. [12] A semiconductor device comprising the printed wiring board of [10]. [13] A semiconductor device comprising the multi-layer flexible substrate of [11]. [Effects of the invention]

According to the present invention, there can be provided a resin composition capable of obtaining a cured product having a suppressed curing shrinkage rate and excellent dielectric constant, a resin sheet containing the resin composition, a printed wiring board having an insulating layer formed using the resin composition, a multilayer flexible substrate, and a semiconductor device.

The present invention will be described in detail below according to its suitable implementation forms. However, the present invention is not limited to the following implementation forms and examples, and can be arbitrarily changed within the scope of the patent application scope of the present invention and its equivalent scope. In addition, the so-called dielectric constant, unless otherwise specified, represents the relative dielectric constant.

[Resin composition] The resin composition of the present invention is a resin composition containing (A) a compound containing an aromatic ester skeleton and an unsaturated bond and (B) a polyimide resin, wherein the content of the component (B) is 10% by mass or more and 50% by mass or less when the non-volatile components in the resin composition are 100% by mass. In the present invention, by containing the component (A) and further containing a predetermined amount of the component (B), a cured product having a suppressed curing shrinkage rate and excellent dielectric constant can be obtained. In addition, a cured product having an excellent dielectric tangent can also be obtained in general.

The resin composition may also be combined with the components (A) and (B) to further include any other components. The optional components include (C) inorganic fillers, (D) thermosetting resins, (E) curing accelerators, and (F) other additives. The following is a detailed description of each component contained in the resin composition.

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

(A) component has an aromatic ester skeleton. The aromatic ester skeleton refers to a skeleton having an ester bond and an aromatic ring bonded to one or both ends of the ester bond, and preferably having an aromatic ring at both ends of the ester bond. As for the group having such a skeleton, for example, there can be mentioned arylcarbonyloxy, aryloxycarbonyl, arylcarbonyloxy, aryloxycarbonyl, arylcarbonyloxyaryl, aryloxycarbonylaryl, arylcarbonyloxyaryl, aryloxycarbonylaryl, etc. In addition, the number of carbon atoms of the group having such a skeleton is preferably 7 to 20, more preferably 7 to 15, and even more preferably 7 to 11. Aromatic hydrocarbon groups such as aryl and aryl may also have substituents.

As for the aryl group, an aryl group having 6 to 30 carbon atoms is preferred, an aryl group having 6 to 20 carbon atoms is more preferred, and an aryl group having 6 to 10 carbon atoms is even more preferred. As for such an aryl group, for example, phenyl, furanyl, pyrrolyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, pyridyl, pyrimidinyl, oxazinyl, pyrazinyl, triazinyl, etc., which are obtained by removing one hydrogen atom from a monocyclic aromatic compound; naphthyl, anthracenyl, phenanthrenyl, quinolyl, isoquinolyl, quinazolinyl, phthalazinyl, pteridinyl, coumarinyl, indolyl, benzimidazolyl, benzopyranyl, acridinyl, etc., which are obtained by removing one hydrogen atom from a condensed ring aromatic compound; and the like.

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 even more preferably an arylene group having 6 to 10 carbon atoms. Examples of such arylene groups include phenylene, naphthylene, anthracenylene, biphenylene (-C ₆ H ₄ -C ₆ H ₄ -) and the like.

Component (A) contains unsaturated bonds. This improves the dielectric constant of the cured product. In addition, unsaturated bonds contribute to the curing reaction of the resin composition. Since unsaturated bonds contribute to the curing reaction, the ester portion of the aromatic ester skeleton can be inhibited from being used in the curing reaction, resulting in the inhibition of the curing shrinkage rate.

The unsaturated bond is preferably a carbon-carbon unsaturated bond. As for the unsaturated bond, it is preferred to have at least one substituent as an unsaturated bond. Examples of the unsaturated bond include unsaturated hydrocarbon groups such as alkenyl groups having 2 to 30 carbon atoms and alkynyl groups having 2 to 30 carbon atoms. It is preferred that the unsaturated bond has a substituent of an aromatic hydrocarbon group as a terminal, and it is more preferred that the unsaturated bond has a substituent of an aromatic hydrocarbon group as both terminals.

Examples of the alkenyl group having 2 to 30 carbon atoms include vinyl, allyl, propenyl, isopropenyl, 1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-octenyl, 2-octenyl, 1-undecenyl, 1-pentadecenyl, 3-pentadecenyl, 7-pentadecenyl, 1-octadecenyl, 2-octadecenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl, 1,3-butadienyl, 1,4-butadienyl, hexa-1,3-dienyl, hexa-2,5-dienyl, pentadeca-4,7-dienyl, hexa-1,3,5-trienyl, and pentadeca-1,4,7-trienyl.

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

Among them, in terms of unsaturated bonds, alkenyl groups having 2 to 30 carbon atoms are preferred, alkenyl groups having 2 to 10 carbon atoms are more preferred, alkenyl groups having 2 to 5 carbon atoms are even more preferred, allyl groups, isopropenyl groups and 1-propenyl groups are even more preferred, and allyl groups are particularly preferred.

The component (A) may have any of an aromatic hydrocarbon group, an aliphatic hydrocarbon group, an oxygen atom, a sulfur atom, and a combination thereof in addition to the aromatic ester skeleton. The term "aromatic hydrocarbon group" means a hydrocarbon group containing an aromatic ring, and the aromatic ring may be monocyclic, polycyclic, or heterocyclic.

As for the aromatic hydrocarbon group, a divalent aromatic hydrocarbon group is preferred, an arylene group and an arylene alkyl group are more preferred, and an arylene group is even more preferred. As for the arylene group, an arylene group having 6 to 30 carbon atoms is preferred, an arylene group having 6 to 20 carbon atoms is more preferred, and an arylene group having 6 to 10 carbon atoms is even more preferred. As for such an arylene group, for example, a phenylene group, a naphthylene group, an anthrylene group, a biphenylene group, etc. are exemplified. As for the arylene alkyl group, an arylene alkyl group having 7 to 30 carbon atoms is preferred, an arylene alkyl group having 7 to 20 carbon atoms is more preferred, and an arylene alkyl group having 7 to 15 carbon atoms is even more preferred. Among these, a phenylene group is even more preferred.

As for the aliphatic alkyl group, a divalent aliphatic alkyl group is preferred, a divalent saturated aliphatic alkyl group is more preferred, an alkylene group and a cycloalkylene group are more preferred. As for the alkylene group, an alkylene group having 1 to 10 carbon atoms is preferred, an alkylene group having 1 to 6 carbon atoms is more preferred, and an alkylene group having 1 to 3 carbon atoms is more preferred. As for the alkylene group, for example, a methylene group, an ethylene group, a propylene group, a 1-methylmethylene group, a 1,1-dimethylmethylene group, a 1-methylethylene group, a 1,1-dimethylethylene group, a 1,2-dimethylethylene group, a butylene group, a 1-methylpropylene group, a 2-methylpropylene group, a pentylene group, a hexylene group, and the like can be cited.

The cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms, more preferably a cycloalkyl group having 3 to 15 carbon atoms, and even more preferably a cycloalkyl group having 5 to 10 carbon atoms. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclopentyl group, a cycloheptyl group, and a cycloalkyl group represented by the following formulas (a) to (d). In formulas (a) to (d), "*" represents a bonding bond.

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

As for the alkyl group having 1 to 10 carbon atoms, for example, there can be mentioned 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, a 1,2-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, but examples thereof include methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentyloxy, hexyloxy, 2-ethylhexyloxy, octyloxy, and nonyloxy.

Halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc. The above-mentioned substituents may further have substituents (hereinafter referred to as "secondary substituents"). The unsaturated hydrocarbon groups are as described above. The secondary substituents may be the same as the above-mentioned substituents unless otherwise specified.

The component (A) is preferably any one of a compound represented by the following general formula (A-1) and a compound represented by the following general formula (A-2). (In general formula (A-1), Ar ¹¹ each independently represents a monovalent aromatic hydrocarbon group which may have a substituent, Ar ¹² each independently represents a divalent aromatic hydrocarbon group which may have a substituent, and Ar ¹³ each independently represents a divalent aromatic hydrocarbon group which may have a substituent, a divalent aliphatic hydrocarbon group which may have a substituent, an oxygen atom, a sulfur atom, or a divalent group composed of a combination thereof. n represents an integer of 0 to 10.) (In general formula (A-2), Ar ²¹ represents an m-valent aromatic hydrocarbon group which may have a substituent, and Ar ²² each independently represents a monovalent aromatic hydrocarbon group which may have a substituent. m represents an integer of 2 or 3.)

In the general formula (A-1), Ar ¹¹ each independently represents a monovalent aromatic alkyl group which may have a substituent. Examples of the monovalent aromatic alkyl group include phenyl, furanyl, pyrrolyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, pyridyl, pyrimidinyl, oxazinyl, pyrazinyl, triazinyl, etc., which are obtained by removing one hydrogen atom from a monocyclic aromatic compound; naphthyl, anthracenyl, phenanthrenyl, quinolyl, isoquinolyl, quinazolinyl, phthalazinyl, pteridinyl, coumarinyl, indolyl, benzimidazolyl, benzopyranyl, acridinyl, etc., which are obtained by removing one hydrogen atom from a condensed ring aromatic compound; and the like. Among them, phenyl is preferred from the viewpoint of significantly obtaining the effect of the present invention. The monovalent aromatic hydrocarbon group represented by Ar ¹¹ may also have a substituent. The substituent is the same as the substituent that may have an aromatic ester skeleton. Among them, it is more preferred that the substituent of Ar ¹¹ contains an unsaturated bond.

In the general formula (A-1), Ar ¹² each independently represents a divalent aromatic hydrocarbon group which may have a substituent. As the divalent aromatic hydrocarbon group, arylene groups and arylene alkyl groups are mentioned, and arylene groups are preferred. As the arylene groups, arylene groups having 6 to 30 carbon atoms are preferred, arylene groups having 6 to 20 carbon atoms are more preferred, and arylene groups having 6 to 10 carbon atoms are even more preferred. As such arylene groups, for example, phenylene groups, naphthylene groups, anthracenylene groups, biphenylene groups, etc. are mentioned. As the arylene alkyl groups, arylene alkyl groups having 7 to 30 carbon atoms are preferred, arylene alkyl groups having 7 to 20 carbon atoms are more preferred, and arylene alkyl groups having 7 to 15 carbon atoms are even more preferred. Among these, phenylene groups are even more preferred.

The divalent aromatic hydrocarbon group represented by ^Ar12 may have a substituent. The substituent is the same as the substituent which may have an aromatic ester skeleton.

In general formula (A-1), Ar ¹³ each independently represents a divalent aromatic hydrocarbon group which may have a substituent, a divalent aliphatic hydrocarbon group which may have a substituent, an oxygen atom, a sulfur atom, or a divalent group formed by a combination thereof, preferably a divalent group formed by a combination thereof. The divalent aromatic hydrocarbon group is the same as the divalent aromatic hydrocarbon group represented by Ar ¹² .

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

As for the alkylene group, an alkylene group having 1 to 10 carbon atoms is preferred, an alkylene group having 1 to 6 carbon atoms is more preferred, and an alkylene group having 1 to 3 carbon atoms is even more preferred. As for the alkylene group, for example, a methylene group, an ethylene group, a propylene group, a 1-methylmethylene group, a 1,1-dimethylmethylene group, a 1-methylethylene group, a 1,1-dimethylethylene group, a 1,2-dimethylethylene group, a butylene group, a 1-methylpropylene group, a 2-methylpropylene group, a pentylene group, a hexylene group, and the like can be cited.

The cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms, more preferably a cycloalkyl group having 3 to 15 carbon atoms, and even more preferably a cycloalkyl group having 5 to 10 carbon atoms. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclopentyl group, a cycloheptyl group, and the cycloalkyl groups represented by the above formulae (a) to (d). The cycloalkyl group represented by the formula (c) is preferred.

As for the divalent groups formed by such combinations, a divalent group formed by combining a divalent aromatic hydrocarbon group which may have a substituent and a divalent aliphatic hydrocarbon group which may have a substituent is preferred, and a divalent group formed by alternately combining a plurality of divalent aromatic hydrocarbon groups which may have a substituent and a plurality of divalent aliphatic hydrocarbon groups which may have a substituent is more preferred. As specific examples of the aforementioned divalent groups, the following divalent groups (A1) to (A8) can be cited. In the formula, a1 to a8 represent integers of 0 to 10, preferably integers of 0 to 5. "*" represents a bond, and the wavy line represents the structure obtained by the reaction of the aromatic compound, the oxyhalogenated product of the aromatic compound, or the esterified product of the aromatic compound used in the synthesis of component (A).

The divalent aromatic hydrocarbon group and divalent aliphatic hydrocarbon group represented by ^Ar13 may have a substituent. The substituent is the same as the substituent that may have an aromatic ester skeleton.

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

In general formula (A-2), Ar ²¹ represents an m-valent aromatic alkyl group which may have a substituent. The m-valent aromatic alkyl group is preferably an m-valent aromatic alkyl group having 6 to 30 carbon atoms, more preferably an m-valent aromatic alkyl group having 6 to 20 carbon atoms, and even more preferably an m-valent aromatic alkyl group having 6 to 10 carbon atoms. The m-valent aromatic alkyl group represented by Ar ²¹ may also have a substituent. The substituent is the same as the substituent which may have an aromatic ester skeleton.

In general formula (A-2), Ar ²² each independently represents a monovalent aromatic hydrocarbon group which may have a substituent. Ar ²² is the same as the aromatic hydrocarbon group represented by Ar ¹¹ in general formula (A-1). The monovalent aromatic hydrocarbon group represented by Ar ²² may also have a substituent. The substituent is the same as the substituent which may have an aromatic ester skeleton.

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

As specific examples of component (A), the following compounds can be cited. In addition, as specific examples of component (A), the compounds described in paragraphs 0068 to 0071 of International Publication No. 2018/235424 and paragraphs 0113 to 0115 of International Publication No. 2018/235425 can be cited. However, component (A) is not limited to these specific examples. In the formula, s represents an integer of 0 or 1 or more, and r represents an integer of 1 to 10.

The component (A) may be synthesized by a known method. The component (A) may be synthesized, for example, by the method of International Publication No. 2018/235424 or International Publication No. 2018/235425.

The weight average molecular weight of the component (A) is preferably 150 or more, more preferably 200 or more, and even more preferably 250 or more, and is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1500 or less, from the viewpoint of significantly obtaining the effect of the present invention. The weight average molecular weight of the component (A) is a weight average molecular weight in terms of polystyrene measured by colloid permeation chromatography (GPC).

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

The content of the component (A) is 0.1% by mass or more, preferably 1% by mass or more, more preferably 3% by mass or more, and 30% by mass or less, preferably 28% by mass or less, and even more preferably 25% by mass or less, 20% by mass or less, 15% by mass or less, or 10% by mass or less, based on 100% by mass of the non-volatile components in the resin composition.

<(B) Polyimide resin> The resin composition contains (B) polyimide resin as the (B) component. By including the (B) component in the resin composition, the cured product becomes soft, and as a result, a cured product with suppressed curing shrinkage and excellent dielectric constant can be obtained.

From the viewpoint of suppressing the curing shrinkage rate, the content of the component (B) is 10% by mass or more, preferably 13% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more, when the non-volatile components in the resin composition are 100% by mass. From the viewpoint of significantly obtaining the desired effect of the present invention, the upper limit is 50% by mass or less, preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 25% by mass or less.

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

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

As for the aliphatic diamine compounds, there can be mentioned linear aliphatic diamine compounds such as 1,2-ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-hexamethylenediamine, 1,5-diaminopentane, 1,10-diaminodecane, etc.; 1,2-diamino-2-methylpropane, 2,3-diamino-2,3-butane and 2 -methyl-1,5-diaminopentane and other branched chain aliphatic diamine compounds; 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine) and other alicyclic diamine compounds; dimer acid type diamine (hereinafter also referred to as "dimer diamine"), etc., among which dimer acid type diamine is more preferred.

The so-called dimer acid type diamine refers to a diamine compound obtained by replacing the two terminal carboxylic acid groups (-COOH) of the dimer acid with aminomethyl (-CH2-NH2) or amino (-NH2). Dimer acid is a known compound obtained by dimerizing unsaturated fatty acids (preferably those with 11 to 22 carbon atoms, particularly preferably those with 18 carbon atoms), and its industrial production process has been almost standardized in the industry. Dimer acid is easily obtained by dimerizing unsaturated fatty acids with 18 carbon atoms such as oleic acid and linoleic acid, which can be obtained very cheaply, to obtain a dimer acid with 36 carbon atoms as the main component. In addition, dimer acid may contain any amount of monomeric acid, trimer acid, other polymerized fatty acids, etc. depending on the production method, the degree of purification, etc. In addition, after the polymerization reaction of unsaturated fatty acids, although double bonds remain, in this specification, hydrogenated products that are further subjected to hydrogenation reaction to reduce the unsaturation are also included in dimer acids. Dimer acid-type diamines are commercially available, such as "PRIAMINE 1073", "PRIAMINE 1074", and "PRIAMINE 1075" manufactured by Croda Japan; "VERSAMINE 551" and "VERSAMINE 552" manufactured by Cognis Japan.

Examples of the aromatic diamine compound include phenylenediamine compounds, naphthalene diamine compounds, and diphenylamine compounds.

The so-called phenylenediamine compound refers to a compound composed of a benzene ring having two amino groups, and the benzene ring here may have 1 to 3 substituents. The substituents here are the same as the substituents that may have an aromatic ester skeleton in the (A) component. Examples of the phenylenediamine compound include 1,4-phenylenediamine, 1,2-phenylenediamine, 1,3-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, 3,5-diaminobiphenyl, and 2,4,5,6-tetrafluoro-1,3-phenylenediamine.

The so-called naphthalene diamine compound refers to a compound composed of a naphthalene ring having two amino groups, and the naphthalene ring here may have 1 to 3 substituents. The substituents here are the same as the substituents that may have an aromatic ester skeleton in the component (A). Examples of the naphthalene diamine compound include 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,6-diaminonaphthalene, 2,3-diaminonaphthalene, etc.

The so-called diphenylamine compound refers to a compound containing two aniline structures in the molecule, and each of the two benzene rings in the two aniline structures may further have 1 to 3 substituents. The substituents here are the same as the substituents that may have an aromatic ester skeleton in the (A) component. The two aniline structures in the diphenylamine compound may be directly bonded and/or may be bonded through one or two connecting structures having 1 to 100 skeleton atoms selected from carbon atoms, oxygen atoms, sulfur atoms and nitrogen atoms. The diphenylamine compound may also include two aniline structures bonded through two bonds.

Specifically, the "connection structure" of the diphenylamine compound includes -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-, -NH-, -Ph-, -Ph-Ph-, -C( _CH3 ) _{2 -} Ph-C(CH3)2-, -O- _Ph -O-, -O-Ph _- SO2-, -NH-, -CONH-, -OCO-, -COO-, -CH2-, -CH2-, -CH2-, -CH2-, -CH2-, _-CH2- -Ph-O-, -O-Ph-C(CH ₃ ) ₂ -Ph-O-, -Ph-CO-O-Ph-, -C(CH ₃ ) ₂ -Ph-C(CH ₃ ) ₂ -, groups represented by the following formulae (I) and (II), and groups formed by combinations thereof. In the present specification, "Ph" represents 1,4-phenylene, 1,3-phenylene or 1,2-phenylene.

In one embodiment, the diphenylamine compound includes, specifically, 4,4'-diamino-2,2'-di-trifluoromethyl-1,1'-biphenyl, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 4-aminophenyl 4-aminobenzoate, 1, 3-Bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 2,2-bis(4-aminophenyl)propane, 4,4'-(hexafluoroisopropylidene)diphenylamine, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, α,α-bis[4-( α,α-Bis[4-(4-aminophenoxy)phenyl]-1,4-diisopropylbenzene, 4,4'-(9-fluorenyl)diphenylamine, 2,2-bis(3-methyl-4-aminophenyl)propane, 2,2-bis(3-methyl-4-aminophenyl)benzene, 4,4'-diamino-3,3'-dimethyl-1,1'-biphenyl , 4,4'-diamino-2,2'-dimethyl-1,1'-biphenyl, 9,9'-bis(3-methyl-4-aminophenyl)fluorene, 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindane, etc., preferably 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindane.

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

(In formula (B-1), R ¹ to R ⁸ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, -X ⁹ -R ⁹ , or -X ¹⁰ -R ¹⁰ , at least one of R ¹ to R ⁸ is -X ¹⁰ -R ¹⁰ , X ⁹ each independently represents a single bond, -NR ^9' -, -O-, -S-, -CO-, -SO ₂ -, -NR ^9' CO-, -CONR ^9' -, -OCO-, or -COO-, R ⁹ each 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, X ¹⁰ each independently represents a single bond, -(substituted or unsubstituted alkylene)-, -NH-, -O-, -S-, -CO-, -SO ₂ -, -NHCO-, -CONH-, -OCO-, or -COO-, and R ¹⁰ each independently represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.)

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

The alkenyl represented by R ⁹ and R ^9' in formula (B-1) refers to a straight chain, branched chain or cyclic monovalent unsaturated hydrocarbon group having at least one carbon-carbon double bond. The alkenyl group is preferably an alkenyl group having 2 to 6 carbon atoms, and more preferably an alkenyl group having 2 or 3 carbon atoms. Examples of such alkenyl groups include vinyl, 1-propenyl, 2-propenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 3-methyl-2-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 4-methyl-3-pentenyl, 1-hexenyl, 3-hexenyl, 5-hexenyl, and 2-cyclohexenyl. The substituents of the alkenyl group in the "substituted or unsubstituted alkenyl group" are not particularly limited, but examples thereof include halogen atoms, cyano groups, alkoxy groups, aryl groups, heteroaryl groups, amino groups, nitro groups, hydroxyl groups, carboxyl groups, sulfonic acid groups, etc. The number of substituents is preferably 1 to 3, and more preferably 1.

The substituents of the alkyl group in the "substituted or unsubstituted alkyl group" and the substituents of the alkenyl group in the "substituted or unsubstituted alkenyl group" are not particularly limited, but examples thereof include halogen atoms, cyano groups, alkoxy groups, amino groups, nitro groups, hydroxyl groups, carboxyl groups, sulfonic acid groups, etc. The number of substituents is preferably 1 to 3, and more preferably 1.

Alkoxy refers to a monovalent group formed by an alkyl group bonded to an oxygen atom (alkyl-O-). As for the alkoxy group, an alkoxy group having 1 to 6 carbon atoms is preferred, and an alkoxy group having 1 to 3 carbon atoms is more preferred. As for such alkoxy groups, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, etc. can be mentioned.

The alkylene group represented by ^X10 in formula (B-1) refers to 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 -CH ₂ -, -CH ₂ -CH ₂ -, -CH(CH ₃ )-, -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH(CH ₃ )-, -CH(CH ₃ )-CH ₂ -, -C(CH ₃ ) ₂ -, -CH ₂ -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH(CH ₃ )-, -CH ₂ -CH(CH ₃ )-CH ₂ -, -CH(CH ₃ )-CH ₂ -CH ₂ -, -CH ₂ -C(CH ₃ ) ₂ -, -C(CH ₃ ) ₂ -CH ₂ -, etc. The substituents of the alkylene group in the "substituted or unsubstituted alkylene group" are not particularly limited, but examples thereof include halogen atoms, cyano groups, alkoxy groups, aryl groups, heteroaryl groups, amino groups, nitro groups, hydroxyl groups, carboxyl groups, sulfonic acid groups, etc. The number of substituents is preferably 1 to 3, and more preferably 1.

The aryl group represented by ^R10 in formula (B-1) is preferably an aryl group having 6 to 14 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms. Examples of such aryl groups include phenyl, 1-naphthyl, 2-naphthyl, etc., and preferably phenyl. The substituent of the aryl group in the "substituted or unsubstituted aryl group" is not particularly limited, but examples thereof include halogen atoms, cyano groups, alkyl groups, alkoxy groups, aryl groups, heteroaryl groups, amino groups, nitro groups, hydroxyl groups, carboxyl groups, sulfonic acid groups, etc. The number of substituents is preferably 1 to 3, and more preferably 1.

The heteroaryl group represented by R ¹⁰ in formula (B-1) refers to an aromatic heterocyclic group having 1 to 4 heteroatoms selected from oxygen atoms, nitrogen atoms and sulfur atoms. The heteroaryl group is preferably a 5-12-membered (preferably 5 or 6-membered) monocyclic, bicyclic or tricyclic (preferably monocyclic) aromatic heterocyclic group. As for such heteroaryl groups, for example, furanyl, 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, oxazinyl, pyrimidinyl, pyrazinyl, triazinyl, etc. The substituents of the heteroaryl group in the "substituted or unsubstituted heteroaryl group" are the same as the substituents of the aryl group in the "substituted or unsubstituted aryl group".

R ¹ to R ⁸ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, -X ⁹ -R ⁹ or -X ¹⁰ -R ¹⁰ . Preferably, ^{R 1} to R ⁸ each independently represent a hydrogen atom or -X ¹⁰ -R ¹⁰ .

At least one of R ¹ to R ⁸ is -X ¹⁰ -R ¹⁰ . Preferably, one or two of R ¹ to R ⁸ are -X ¹⁰ -R ¹⁰ , more preferably, one or two of R ⁵ to R ⁸ are -X ¹⁰ -R ¹⁰ , and even more preferably, one or two of R ⁵ and R ⁷ are -X ¹⁰ -R ¹⁰ .

In one embodiment, preferably, one or two of R ¹ to R ⁸ are -X ¹⁰ -R ¹⁰ , and the others of R ¹ to R ⁸ are hydrogen atoms. More preferably, one or two of R ⁵ to R ⁸ are -X ¹⁰ -R ¹⁰ , and the others of R ¹ to R ⁸ are hydrogen atoms. Even more preferably, one or two of R ⁵ and R ⁷ are -X ¹⁰ -R ¹⁰ , and the others of R ¹ to R ⁸ are hydrogen atoms.

X ⁹ each independently represents a single bond, -NR ^9'- , -O-, -S-, -CO-, -SO ₂ -, -NR 9'CO-, -CONR ^9'- , -OCO-, or -COO-. R ⁹ each independently represents a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group. ^{X 9} is preferably a single bond.

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

^X10 each independently represents a single bond, -(substituted or unsubstituted alkylene)-, -NH-, -O-, -S-, -CO-, _-SO2- , -NHCO-, -CONH-, -OCO-, or -COO-. ^X10 is preferably a single bond.

R ¹⁰ each independently represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. R ¹⁰ is preferably a substituted or unsubstituted aryl group.

In one embodiment, the diamine compound is represented by formula (B-1), preferably the compound represented by the following formula (B-2), and more preferably the compound represented by the following formula (B-3) (4-aminobenzoic acid 5-amino-1,1'-biphenyl-2-ester). (In the formula, R ¹ to R ⁶ and R ⁸ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, or -X ⁹ -R ^{9 , and} other symbols are the same as those in formula (B-1).)

The diamine compound may be commercially available or may be synthesized by a known method. For example, the diamine compound represented by formula (B-1) may be synthesized by the synthesis method described in Patent No. 6240798 or a method in accordance therewith. The diamine compound may be used alone or in combination of two or more.

The acid anhydride used to prepare the component (B) is not particularly limited, but in a preferred embodiment, it is an aromatic tetracarboxylic dianhydride. Examples of the aromatic tetracarboxylic dianhydride include benzenetetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, anthracenetetracarboxylic dianhydride, and diphthalic dianhydride, and diphthalic dianhydride is preferred.

The so-called benzene tetracarboxylic dianhydride means a benzene dianhydride having four carboxyl groups, and the benzene ring here may have 1 to 3 substituents. The substituents are preferably selected from halogen atoms, cyano groups and -X ¹³ -R ¹³ (same as the definition of the following formula (B-4)). Specific examples of benzene tetracarboxylic dianhydride include pyromellitic dianhydride and 1,2,3,4-benzenetetracarboxylic dianhydride.

Naphthalenetetracarboxylic dianhydride refers to naphthalene dianhydride having four carboxyl groups, and the naphthalene ring here may have 1 to 3 substituents. The substituents are preferably selected from halogen atoms, cyano groups, and -X ¹³ -R ¹³ (same as the definition of the following formula (B-4)). Specific examples of naphthalenetetracarboxylic dianhydride include 1,4,5,8-naphthalenetetracarboxylic dianhydride and 2,3,6,7-naphthalenetetracarboxylic dianhydride.

The so-called anthracenetetracarboxylic dianhydride refers to an anthracene dianhydride having four carboxyl groups, and the anthracene ring here may optionally have 1 to 3 substituents. The substituents are preferably selected from halogen atoms, cyano groups, and -X ¹³ -R ¹³ (same as defined in the following formula (B-4)). Specific examples of anthracenetetracarboxylic dianhydride include 2,3,6,7-anthracenetetracarboxylic dianhydride.

The so-called diphthalic anhydride means a compound containing two anhydrous phthalic acids in the molecule, and the two benzene rings in the two anhydrous phthalic acids may each have 1 to 3 substituents. Here, the substituents are preferably selected from halogen atoms, cyano groups and -X ¹³ -R ¹³ (same as the definition of the following formula (B-4)). The two anhydrous phthalic acids in diphthalic anhydride are directly bonded or bonded via a connecting structure having 1 to 100 skeleton atoms selected from carbon atoms, oxygen atoms, sulfur atoms and nitrogen atoms.

As for the diphthalic dianhydride, there can be mentioned, for example, a compound represented by formula (B-4). (In the formula, R ¹¹ and R ¹² each independently represent a halogen atom, a cyano group, a nitro group or -X ¹³ -R ¹³ , X ¹³ each independently represents a single bond, -NR ^13' -, -O-, -S-, -CO-, -SO ₂ -, -NR ^13' CO-, -CONR ^13' -, -OCO-, or -COO-, R ¹³ each 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 structure that can be connected through 1 to 100 skeleton atoms selected from carbon atoms, oxygen atoms, sulfur atoms and nitrogen atoms, and n1 and m1 each independently represent an integer of 0 to 3.)

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

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

Specific examples of the "connecting structure" in Y include _-CH2- , _{-CH2CH2- ,} -CH2CH2CH2-, -CH2CH2CH2CH2-, _{-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- and the like.

As for the phthalic acid dianhydride, specifically, 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic acid dianhydride, 3,3',4,4'-diphenyl sulfonate tetracarboxylic acid dianhydride, 3,3',4,4'-biphenyl tetracarboxylic acid dianhydride, 2,2',3,3'-biphenyl tetracarboxylic acid dianhydride, 2,3,3',4'-biphenyl tetracarboxylic acid dianhydride, 2,3,3',4'-benzophenone tetracarboxylic acid dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic acid dianhydride, 2,3,3',4'-diphenyl sulfonate tetracarboxylic acid dianhydride, 2,2'-bis(3,4-dicarboxyphenoxyphenyl)sulfonate dianhydride, methylene-4,4'-phthalic acid dianhydride, 1,1-ethylene-4,4'-phthalic acid dianhydride, 2,2 -propylene-4,4'-diphthalic acid dianhydride, 1,2-ethylene-4,4'-diphthalic acid dianhydride, 1,3-trimethylene-4,4'-diphthalic acid dianhydride, 1,4-tetramethylene-4,4'-diphthalic acid dianhydride, 1,5-pentamethylene-4,4'-diphthalic acid dianhydride, 1,3-bis(3,4-dicarboxyphenyl)phthalic acid dianhydride, 1,4- Bis(3,4-dicarboxyphenyl)phthalic anhydride, 1,3-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 1,4-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 4,4'-(4,4'-isopropylidene diphenoxy)phthalic acid dianhydride, etc.

Aromatic tetracarboxylic dianhydrides may be commercially available or may be synthesized by a known method or a method in accordance therewith. Aromatic tetracarboxylic dianhydrides may be used alone or in combination of two or more.

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

As other acid anhydrides, specifically, there can be mentioned 1,2,3,4-cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, 3,3′,4,4′-biscyclohexyltetracarboxylic dianhydride, carbonyl-4,4′-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene-4,4′- Aliphatic tetracarboxylic acid dianhydrides such as 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-4,4'-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 aromatic tetracarboxylic dianhydride in the entire structure derived from the acid anhydride constituting the component (B) is preferably 10 mol% or more, more preferably 30 mol% or more, even more preferably 50 mol% or more, even more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably 100 mol%.

The component (B) preferably has a structural unit represented by the following general formula (B). (In general formula (B), R ⁵¹ represents a single bond or a residue derived from an acid anhydride, and R ⁵² represents a single bond or a residue derived from a diamine compound.)

R ⁵¹ represents a single bond or a residue derived from an acid anhydride, preferably a residue derived from an acid anhydride. The residue derived from an acid anhydride represented by R ⁵¹ refers to a divalent group obtained by removing two oxygen atoms from an acid anhydride. The acid anhydride is as described above.

R ⁵² represents a single bond or a residual group derived from a diamine compound, preferably a residual group derived from a diamine compound. The residual group derived from a diamine compound represented by R ⁵² refers to a divalent group obtained by removing two amino groups from the diamine compound. The diamine compound is as described above.

The component (B) can be prepared by a conventionally known method. As for the conventionally known method, for example, a method of heating a mixture of a diamine compound, an acid anhydride and a solvent to react. The mixing amount of the diamine compound can be, for example, generally 0.5 to 1.5 molar equivalents, preferably 0.9 to 1.1 molar equivalents, relative to the acid anhydride.

As the solvent for preparing the (B) component, there can be mentioned amide solvents such as N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylformamide, and N-methyl-2-pyrrolidone; ketone solvents such as acetone, methyl ethyl ketone (MEK), and cyclohexanone; ester solvents such as γ-butyrolactone; and hydrocarbon solvents such as cyclohexane and methylcyclohexane. In the preparation of the (B) component, an imidization catalyst, an azeotropic dehydration solvent, an acid catalyst, etc. can also be used as needed. As for the imidization catalyst, tertiary amines such as triethylamine, triisopropylamine, triethylenediamine, N-methylpyrrolidine, N-ethylpyrrolidine, N,N-dimethyl-4-aminopyridine, pyridine, etc. can be mentioned. As for the azeotropic dehydration solvent, toluene, xylene, ethylcyclohexane, etc. can be mentioned. As for the acid catalyst, anhydrous acetic acid, etc. can be mentioned. The amount of imidization catalyst, azeotropic dehydration solvent, acid catalyst, etc. used can be appropriately set by the industry familiar with the field. The reaction temperature for the preparation of component (B) is usually 100~250℃.

The weight average molecular weight of the component (B) is preferably 1,000 or more, more preferably 5,000 or more, and further preferably 10,000 or more, and is preferably 100,000 or less, more preferably 70,000 or less, and further preferably 50,000 or less.

When the content of component (A) is a1 when the non-volatile components in the resin composition are 100 mass %, and when the content of component (B) is b1 when the non-volatile components in the resin composition are 100 mass %, a1/b1 is preferably 0.1 or more, more preferably 0.15 or more, and even more preferably 0.2 or more, and preferably 1 or less, more preferably 0.5 or less, and even more preferably 0.3 or less. By adjusting a1/b1 within this range, the effect of the present invention can be significantly obtained.

<(C) Inorganic filler> In addition to the above components, the resin composition may further contain an inorganic filler as the (C) component.

Inorganic compounds are used as materials of the inorganic filler. Examples of materials of the inorganic filler include silicon oxide, aluminum oxide, glass, diatomite, silicate, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silicon oxide is particularly suitable. Examples of silicon oxide include amorphous silicon oxide, molten silicon oxide, crystalline silicon oxide, synthetic silicon oxide, and hollow silicon oxide. In addition, spherical silicon oxide is preferred. (C) The inorganic filler may be used alone or in combination of two or more.

Commercially available products of component (C) include, for example, "UFP-30" manufactured by Denka; "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumitomo Metal Materials Corporation; "YC100C", "YA050C", "YA050C-MJE", and "YA010C" manufactured by Admatechs; "Silfil NSS-3N", "Silfil NSS-4N", and "Silfil NSS-5N" manufactured by Tokuyama; "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1" manufactured by Admatechs, etc.

The specific surface area of the component (C) is preferably 1 m ² /g or more, more preferably 2 m ² /g or more, and particularly preferably 3 m ² /g or more. The upper limit is not particularly limited, but is preferably 60 m ² /g or less, 50 m ² /g or less, or 40 m ² /g or less. The specific surface area is calculated by the BET multipoint method using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) to adsorb nitrogen on the sample surface.

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, preferably 5 μm or less, more preferably 2 μm or less, and even more preferably 1 μm or less, from the viewpoint of remarkably obtaining the desired effect of the present invention.

The average particle size of component (C) can be measured by laser diffraction and scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be made on a volume basis by using a laser diffraction and scattering particle size distribution measuring device, and the median diameter is used as the average particle size for measurement. The measurement sample can be 100 mg of inorganic filler and 10 g of methyl ethyl ketone weighed into a small glass bottle and dispersed by ultrasound for 10 minutes. The sample is measured using a laser diffraction particle size distribution measuring device, and the wavelength of the light source used is divided into blue and red. The volume-based particle size distribution of the inorganic filler is measured by a flow cell method, and the average particle size is calculated from the obtained particle size distribution as the median diameter. As for the laser diffraction particle size distribution measuring device, for example, there is the "LA-960" manufactured by Horiba, Ltd.

From the viewpoint of improving moisture resistance and dispersibility, component (C) is preferably treated with a surface treatment agent. Examples of the surface treatment agent include vinyl silane coupling agents, (meth) acrylic coupling agents, fluorine-containing silane coupling agents, amino silane coupling agents, epoxy silane coupling agents, butyl silane coupling agents, silane coupling agents, alkoxy silane, organic silazane compounds, and titanium salt coupling agents. Among them, from the viewpoint of significantly obtaining the effect of the present invention, vinyl silane coupling agents, (meth) acrylic coupling agents, and amino silane coupling agents are preferred. The surface treatment agent may be used alone or in combination of two or more.

Commercially available products of surface treatment agents include, for example, "KBM1003" (vinyl triethoxysilane) manufactured by Shin-Etsu Chemical Industries, Ltd., "KBM503" (3-methacryloxypropyl triethoxysilane) manufactured by Shin-Etsu Chemical Industries, Ltd., "KBM403" (3-glycidoxypropoxytrimethoxysilane) manufactured by Shin-Etsu Chemical Industries, Ltd., "KBM803" (3-butyl propyl trimethoxysilane) manufactured by Shin-Etsu Chemical Industries, Ltd., and "KBE903" (3-aminopropyl trimethoxysilane) manufactured by Shin-Etsu Chemical Industries, Ltd. "KBM-573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-4803" (long-chain epoxy-type silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., etc.

From the perspective of improving the dispersibility of the inorganic filler, the degree of surface treatment by the surface treatment agent is preferably within a predetermined range. Specifically, 100 parts by weight of the inorganic filler is preferably treated with 0.2 to 5 parts by weight of the surface treatment agent, more preferably 0.2 to 3 parts by weight, and even more preferably 0.3 to 2 parts by weight.

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. From the perspective of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/ ^m2 or more, more preferably 0.1 mg/ ^m2 or more, and more preferably 0.2 mg/ ^m2 or more. On the other hand, from the perspective of suppressing the increase in the melt viscosity of the resin coating and the melt viscosity in the form of a sheet, it is preferably 1 mg/ ^m2 or less, more preferably 0.8 mg/m2 or ^less , and more preferably 0.5 mg/ ^m2 or less.

The amount of carbon per unit surface area of the inorganic filler can be measured by washing the surface treated inorganic filler with a solvent (e.g. methyl ethyl ketone (MEK)). Specifically, the solvent is to add a sufficient amount of MEK to the inorganic filler that has been surface treated with the surface treatment agent, and then ultrasonically wash it at 25°C for 5 minutes. After removing the supernatant and drying the solid components, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. For the carbon analyzer, the "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, and even more preferably 50% by mass or more, and is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less, when the non-volatile components in the resin composition are 100% by mass.

When the content of component (A) is a1 when the non-volatile components in the resin composition are 100 mass %, the content of component (B) is b1 when the non-volatile components in the resin composition are 100 mass %, and the content of component (C) is c1 when the non-volatile components in the resin composition are 100 mass %, (a1+b1)/c1 is preferably more than 0.4, more preferably 0.43 or more, more preferably 0.45 or more, preferably 1 or less, more preferably 0.6 or less, and even more preferably 0.55 or less. By adjusting (a1+b1)/c1 to be within this range, the effect of the present invention can be significantly obtained.

<(D) Thermosetting resin> In addition to the above-mentioned components, the resin composition may further contain a thermosetting resin as the (D) component. However, components equivalent to (A) to (B) are excluded. Examples of the (D) thermosetting resin include epoxy resins, phenol resins, naphthol resins, benzoxazine resins, active ester resins, cyanate resins, carbodiimide resins, amine resins, and acid anhydride resins. The (D) component may be used alone or in combination of two or more in any ratio. The following are resins that can react with epoxy resins to harden the resin composition, such as phenol resins, naphthol resins, benzoxazine resins, active ester resins, cyanate resins, carbodiimide resins, amine resins, and acid anhydride resins, and are generally referred to as "hardeners".

As for the epoxy resin of the component (D), for example, there can be mentioned bis(xylenol) type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, phenol type epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-benzene type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, The epoxy resin may be a glycidylamine type epoxy resin, a glycidyl ester type epoxy resin, a 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 epoxy resin, a spirocyclic epoxy resin, an oxime type epoxy resin, an oxime dimethanol type epoxy resin, a naphthyl ether type epoxy resin, a trihydroxymethyl type epoxy resin, a tetraphenylethane type epoxy resin, etc. The epoxy resin may be used alone or in combination of two or more.

The resin composition preferably contains an epoxy resin having two or more epoxy groups in one molecule as component (D). From the viewpoint of remarkably obtaining the desired effect of the present invention, the ratio of the epoxy resin having two or more epoxy groups in one molecule of component (D) relative to 100% by mass of the non-volatile component is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

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

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

As liquid epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, alicyclic epoxy resins having an ester skeleton, cyclohexane type epoxy resins, cyclohexanedimethanol type epoxy resins, glycidyl amine type epoxy resins and epoxy resins having a butadiene structure are preferred, and bisphenol A type epoxy resins and bisphenol F type epoxy resins are more preferred.

Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene-based epoxy resins) manufactured by DIC Corporation; "828US", "jER828EL", "825", and "EPIKOTE" manufactured by Mitsubishi Chemical Corporation; "828EL" (bisphenol A type epoxy resin); "jER807" and "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630" and "630LSD" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ZX1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel Chemical & Materials Corporation; Nagase "EX-721" (glycidyl ester type epoxy resin) manufactured by ChemteX; "CELLOXIDE2021P" (lipidic epoxy resin with ester skeleton) manufactured by Daicel; "PB-3600" (epoxy resin with butadiene structure) manufactured by Daicel; "ZX1658" and "ZX1658GS" (liquid 1,4-glycidyl cyclohexane type epoxy resin) manufactured by Nippon Steel Chemical & Materials Co., Ltd. These can be used alone or in combination of two or more.

As the solid epoxy resin, preferably, one having three or more epoxy groups in one molecule is used, and more preferably, an aromatic solid epoxy resin having three or more epoxy groups in one molecule is used.

As solid epoxy resins, dixylenol type epoxy resins, naphthalene type epoxy resins, naphthalene type tetrafunctional epoxy resins, cresol novolac type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol type epoxy resins, biphenyl type epoxy resins, naphthyl ether type epoxy resins, anthracene type epoxy resins, bisphenol A type epoxy resins, bisphenol AF type epoxy resins, and tetraphenylethane type epoxy resins are preferred, and naphthalene type epoxy resins are more preferred.

As solid epoxy resins, naphthalene-type tetrafunctional epoxy resins, cresol novolac-type epoxy resins, dicyclopentadiene-type epoxy resins, trisphenol-type epoxy resins, naphthol-type epoxy resins, biphenyl-type epoxy resins, naphthyl ether-type epoxy resins, anthracene-type epoxy resins, bisphenol A-type epoxy resins, and tetraphenylethane-type epoxy resins are preferred, and naphthalene-type tetrafunctional epoxy resins, naphthol-type epoxy resins, and biphenyl-type epoxy resins are more preferred. Specific examples of solid epoxy resins include "HP4032H" (naphthalene-based epoxy resin), "HP-4700", "HP-4710" (naphthalene-based tetrafunctional epoxy resin), "N-690" (cresol novolac-based epoxy resin), "N-695" (cresol novolac-based epoxy resin), "HP-7200", "HP-7200HH", "HP-7200H" manufactured by DIC Corporation. (dicyclopentadiene epoxy resin), DIC's "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthyl ether epoxy resin); Nippon Kayaku's "EPPN-502H" (triphenylphenol epoxy resin), "NC7000L" (naphthol novolac epoxy resin), "N C3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin); "ESN475V" (naphthalene type epoxy resin), "ESN485" (naphthol novolac type epoxy resin) made by Nippon Steel Chemical & Materials Co., Ltd.; "YX4000H", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (double double epoxy resin) made by Mitsubishi Chemical Corporation. Cresol type epoxy resin), "YX8800" (anthracene type epoxy resin); "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., "YL7760" (bisphenol AF type epoxy resin), "YL7800" (fluorene type epoxy resin), "jER1010" (solid bisphenol A type epoxy resin), "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. These can be used alone or in combination of two or more.

In terms of component (D), when a liquid epoxy resin and a solid epoxy resin are used in combination, the mass ratio (liquid epoxy resin: solid epoxy resin) is preferably 1:0.1 to 1:20, more preferably 1:0.3 to 1:15, and particularly preferably 1:1 to 1:10. By keeping the mass ratio of the liquid epoxy resin to the solid epoxy resin within this range, the desired effect of the present invention can be significantly obtained. Furthermore, when it is usually used in the form of a resin sheet, it can have moderate adhesion. Also, when it is usually used in the form of a resin sheet, sufficient flexibility can be obtained and the operability will be improved. Furthermore, a hardened material having a very high breaking strength is usually obtained.

(D) The epoxy equivalent of the epoxy resin of the component is preferably 50 g/eq. to 5000 g/eq., more preferably 50 g/eq. to 3000 g/eq., still more preferably 80 g/eq. to 2000 g/eq., and still more preferably 110 g/eq. to 1000 g/eq. Within this range, the crosslinking density of the cured product of the resin composition will have a sufficient cured body. The epoxy equivalent is the mass of the epoxy resin containing 1 equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

The weight average molecular weight (Mw) of the epoxy resin of the component (D) is preferably 100 to 5000, more preferably 250 to 3000, and even more preferably 400 to 1500 from the viewpoint of significantly 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 colloid permeation chromatography (GPC).

The content of the epoxy resin in the component (D) is preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more, from the viewpoint of obtaining a cured product showing good mechanical strength and insulation reliability, when the non-volatile components in the resin composition are 100% by mass. The upper limit of the content of the epoxy resin is preferably 40% by mass or less, more preferably 30% by mass or less, and particularly preferably 25% by mass or less, from the viewpoint of significantly obtaining the desired effect of the present invention.

As for the component (D), the ratio of the amount of the epoxy resin to the component (A) is [the total number of epoxy groups in the epoxy resin]: [the total number of unsaturated bonds in the component (A)], preferably in the range of 1:0.01 to 1:5, more preferably 1:0.03 to 1:3, and even more preferably 1:0.05 to 1:1. Here, the so-called "number of epoxy groups in the epoxy resin" is the total value obtained by dividing the mass of the non-volatile components of the epoxy resin in the resin composition by the epoxy equivalent. The "unsaturated bond number of component (A)" is the total value of all values obtained by dividing the mass of the non-volatile components of component (A) in the resin composition by the unsaturated bond equivalent. By making the amount ratio of the epoxy resin to component (A) within this range, the effect of the present invention can be significantly obtained.

When the content of the component (A) is a1 when the non-volatile components in the resin composition are 100 mass %, and when the content of the epoxy resin in the component (D) is d1 when the non-volatile components in the resin composition are 100 mass %, d1/a1 is preferably 1 or more, more preferably 3 or more, and even more preferably 4 or more, and preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. By adjusting d1/a1 to be within this range, the effect of the present invention can be significantly obtained.

As for the active ester resin of component (D), a resin having one or more active ester groups in one molecule can be used. Among them, as for the active ester resin, a resin having two or more highly reactive ester groups such as phenol esters, thiophenol esters, N-hydroxylamine esters, esters of heterocyclic hydroxyl compounds, etc. in one molecule is preferred. The active ester resin is preferably 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 preferred, and an active ester resin obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is even preferred.

As the carboxylic acid compound, for example, benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid and the like can be mentioned.

As for the phenol compound or naphthol compound, for example, hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, hydroquinone, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, 1,3,5-benzenetriol, 1,2,4-benzenetriol, dicyclopentadiene-type diphenol compounds, phenol novolac, etc. can be mentioned. Here, the so-called "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two phenol molecules into one dicyclopentadiene molecule.

Preferred specific examples of active ester resins include active ester resins containing dicyclopentadiene diphenol structures, active ester resins containing naphthalene structures, active ester resins containing acetylated phenol novolacs, and active ester resins containing benzoylated phenol novolacs. Among them, active ester resins containing naphthalene structures and active ester resins containing dicyclopentadiene diphenol structures are more preferred. The so-called "dicyclopentadiene diphenol structure" refers to a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

As for commercially available active ester resins, "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L-65TM" (manufactured by DIC Corporation) can be cited as active ester resins containing dicyclopentadiene-type diphenol structures; "EXB9416-70BK", "EXB-8100L-65T", "EXB-8150L-65T", "EXB-8150-62T", "HPC-8150-60T", "HPC-8150-62T" (manufactured by DIC Corporation) can be cited as active ester resins containing naphthalene structures. Resins; "DC808" (manufactured by Mitsubishi Chemical Co.) can be cited as an active ester resin containing an acetylated product of phenol novolac; "YLH1026" (manufactured by Mitsubishi Chemical Co.) can be cited as an active ester resin containing a benzoylated product of phenol novolac; "DC808" (manufactured by Mitsubishi Chemical Co.) can be cited as an active ester resin containing an acetylated product of phenol novolac Active ester resins of acylated products; "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation) as active ester resins of benzoylated products of phenol novolac; and "EXB-8500-65T" (manufactured by DIC Corporation), etc. can be cited.

As for the phenolic resin and naphthol resin of the component (D), those having a novolac structure are preferred from the viewpoint of heat resistance and water resistance. Furthermore, from the viewpoint of adhesion to the conductive layer, nitrogen-containing phenolic hardeners are preferred, and phenolic resins containing a triazine skeleton are more preferred.

Specific examples of phenol-based resins and naphthol-based resins include "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Chemicals, "NHN", "CBN", and "GPH" manufactured by Nippon Kayaku Co., Ltd., "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V", "SN375", and "SN395" manufactured by Nippon Steel Chemicals & Materials Co., Ltd., and "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", and "EXB-9500" manufactured by DIC Corporation.

Specific examples of the benzoxazine resin of the component (D) include "JBZ-OD100" (benzoxazine ring equivalent: 218), "JBZ-OP100D" (benzoxazine ring equivalent: 218), and "ODA-BOZ" (benzoxazine ring equivalent: 218) manufactured by JFE Chemicals; "P-d" (benzoxazine ring equivalent: 217) and "F-a" (benzoxazine ring equivalent: 217) manufactured by Shikoku Chemical Industries; and "HFB2006M" (benzoxazine ring equivalent: 432) manufactured by Showa High Polymer Co., Ltd.

As for the cyanate resin of the component (D), for example, bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanate)phenylpropane, Bifunctional cyanate resins such as bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanate-phenyl-1-(methylethylidene))benzene, bis(4-cyanate-phenyl)sulfide and bis(4-cyanate-phenyl)ether; polyfunctional cyanate resins derived from phenol novolac and cresol novolac; partially triazine prepolymers of these cyanate resins; etc. Specific examples of cyanate resins include "PT30", "PT30S" and "PT60" (phenol novolac type multifunctional cyanate resins), "ULL-950S" (multifunctional cyanate resin), "BA230", "BA230S75" (prepolymers of bisphenol A dicyanate partially or completely triazine-treated to form trimers) manufactured by Lonza Japan Co., Ltd.

Specific examples of the carbodiimide resin of the component (D) include CARBODILITE (registered trademark) V-03 (carbodiimide equivalent: 216, V-05 (carbodiimide equivalent: 216), V-07 (carbodiimide equivalent: 200), and V-09 (carbodiimide equivalent: 200) manufactured by Nisshinbo Chemical Co., Ltd.; and Stabaxol (registered trademark) P (carbodiimide equivalent: 302) manufactured by Rhein Chemie.

As for the amine resin of the component (D), there can be cited resins having one or more amine groups in one molecule, such as aliphatic amines, polyether amines, alicyclic amines, aromatic amines, etc. Among them, aromatic amines are preferred from the viewpoint of exerting the desired effect of the present invention. The amine resin is preferably a primary amine or a secondary amine, and a primary amine is more preferred. Specific examples of amine resins include 4,4'-methylenebis(2,6-dimethylaniline), diphenyldiaminosulfonate, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfonate, 3,3'-diaminodiphenylsulfonate, m-phenylenediamine, m-dimethylphenylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino -4-hydroxyphenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, and the like. Amine resins that can be used are commercially available products, for example, "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD A-A", "KAYAHARD A-B", "KAYAHARD A-S" manufactured by Nippon Kayaku Co., Ltd., and "EPICURE W" manufactured by Mitsubishi Chemical Corporation.

As for the acid anhydride resin of the component (D), there can be mentioned resins having one or more acid anhydride groups in one molecule. Specific examples of the acid anhydride resin include anhydrous phthalic acid, anhydrous tetrahydrophthalic acid, anhydrous hexahydrophthalic acid, anhydrous methyltetrahydrophthalic acid, anhydrous methylhexahydrophthalic acid, methylnadic anhydride, hydrogenated methylnadic anhydride, anhydrous trialkyltetrahydrophthalic acid, anhydrous dodecenylsuccinic acid, 5-(2,5-dioxotetrahydropyranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, anhydrous trimellitic acid, anhydrous pyromellitic acid, Benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxyphthalic dianhydride, 3,3'-4,4'-diphenylsulfonate tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxy-3-pyranyl)-naphtho[1,2-c]furan-1,3-dione, ethylene glycol bis(trimellitic anhydride), styrene-maleic acid resin obtained by copolymerization of styrene and maleic acid, and other polymer-type acid anhydrides.

In terms of component (D), when epoxy resin and hardener are contained, the amount ratio of epoxy resin to all hardeners is preferably in the range of 1:0.01 to 1:5, more preferably 1:0.3 to 1:3, and even more preferably 1:0.5 to 1:2, in terms of [total number of epoxy groups of epoxy resin]: [total number of reactive groups of hardener]. Here, the so-called "number of epoxy groups of epoxy resin" refers to the total value of the mass of non-volatile components of epoxy resin in the resin composition divided by the epoxy equivalent. The so-called "active base number of the hardener" is the total value of the non-volatile component mass of the hardener in the resin composition divided by the active base equivalent. As for the (D) component, a hardened body with excellent flexibility can be obtained by making the amount ratio of the epoxy resin and the hardener within this range.

The content of the hardener in the component (D) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less, relative to 100% by mass of the non-volatile components in the resin composition, from the viewpoint of obtaining a hardened body having excellent flexibility.

From the viewpoint of obtaining a hardened body having excellent flexibility, the content of the component (D) is preferably 5 mass % or more, more preferably 10 mass % or more, and even more preferably 15 mass % or more, and is preferably 35 mass % or less, more preferably 30 mass % or less, and even more preferably 25 mass % or less, relative to 100 mass % of the non-volatile components in the resin composition.

<(E) Curing accelerator> In addition to the above components, the resin composition may further contain a curing accelerator as the (E) component as an arbitrary component. By containing the (E) component, polymerization by heat can be further accelerated.

As for the component (E), there can be mentioned epoxy resin curing accelerators such as phosphorus curing accelerators, amine curing accelerators, imidazole curing accelerators, guanidine curing accelerators, and metal curing accelerators; and thermal polymerization curing accelerators such as peroxide curing accelerators. The component (E) may be used alone or in combination of two or more.

Phosphorus-based hardening accelerators include, for example, triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, etc., with triphenylphosphine and tetrabutylphosphonium decanoate being preferred.

As for the amine-based hardening accelerator, there can be mentioned trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc., with 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene being preferred.

As for the imidazole hardening accelerator, for example, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2- Methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazole trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino -6-[2'-undecyl imidazolyl-(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 cyanuric acid adduct, 2-phenylimidazole cyanuric acid adduct, 2-phenyl-4,5-dihydroxy Imidazole compounds such as methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazole chloride, 2-methylimidazoline, 2-phenylimidazoline, and adducts of imidazole compounds with epoxy resins, preferably 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole.

As the imidazole-based hardening accelerator, a commercially available product may be used, for example, "P200-H50" manufactured by Mitsubishi Chemical Corporation.

As for the guanidine-based hardening accelerator, for example, cyanamide, 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-methylbiguanidine, 1-ethylbiguanidine, 1-n-butylbiguanidine, 1-n-octadecylbiguanidine, 1,1-dimethylbiguanidine, 1,1-diethylbiguanidine, 1-cyclohexylbiguanidine, 1-allylbiguanidine, 1-phenylbiguanidine, 1-(o-tolyl)biguanidine, etc., preferably dicyanamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene.

As the metal hardening accelerator, there can be mentioned metals, organic metal complexes or organic metal salts 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 compounds and cobalt (III) acetylacetonate compounds, organic copper complexes such as copper (II) acetylacetonate compounds, organic zinc complexes such as zinc (II) acetylacetonate compounds, organic iron complexes such as iron (III) acetylacetonate compounds, organic nickel complexes such as nickel (II) acetylacetonate compounds, and organic manganese complexes such as manganese (II) acetylacetonate compounds. As for the organic metal salt, for example, zinc octylate, tin octylate, zinc cycloalkanoate, cobalt cycloalkanoate, tin stearate, zinc stearate, etc. can be mentioned.

As peroxide-based hardening accelerators, there may be mentioned peroxides such as di-t-butyl peroxide, t-butyl isopropyl peroxide, t-butyl peroxyacetate, α,α'-di(t-butylperoxy)diisopropylbenzene, t-butyl peroxylaurate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyneodecanoate, and t-butylperoxybenzoate.

Examples of commercially available peroxide-based hardening accelerators include "PERHEXYL D", "PERBUTYL C", "PERBUTYL A", "PERBUTYL P", "PERBUTYL L", "PERBUTYL O", "PERBUTYL ND", "PERBUTYL Z", "PERCUMYL P", and "PERCUMYL D" manufactured by NOF Corporation.

From the viewpoint of remarkably obtaining the desired effect of the present invention, the content of the component (E) is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and even more preferably 0.3% by mass or more, and is preferably 1% by mass or less, more preferably 0.8% by mass or less, and even more preferably 0.5% by mass or less, based on 100% by mass of the non-volatile component in the resin composition.

<(F) Other additives> In addition to the above-mentioned components, the resin composition may further contain other additives in any of the components. Such additives include, for example, thermoplastic resins other than component (B), thickeners, defoamers, leveling agents, adhesion-imparting agents, and other resin additives. Such additives may be used alone or in combination of two or more. The content of each can be appropriately set by a person familiar with the field.

The method for preparing the resin composition of the present invention is not particularly limited, and examples thereof include a method of adding a solvent as needed and mixing, dispersing and blending the components using a rotary mixer.

<Physical properties and uses of resin composition> The resin composition contains component (A) and a predetermined amount of component (B). This can suppress the curing shrinkage rate and further obtain a cured product with excellent dielectric constant. In addition, a cured product with excellent dielectric tangent can also be obtained.

The cured product formed by heat curing the resin composition at 190°C for 90 minutes will show the characteristic of low curing shrinkage. That is, the curing shrinkage will be suppressed, thereby obtaining an insulating layer that can suppress warping. The curing shrinkage is preferably 0.35% or less, more preferably 0.34% or less, and even more preferably 0.33% or less. The lower limit of the curing shrinkage is not particularly limited, and can be 0.01% or more. The curing shrinkage can be measured according to the method described in the embodiments described below.

The cured product formed by heat curing the resin composition at 190°C for 90 minutes will show the characteristic of low dielectric constant. Therefore, the cured product has an insulating layer with low dielectric constant. The dielectric constant is preferably 3.0 or less, more preferably 2.9 or less, and even more preferably 2.85 or less. The lower limit of the dielectric constant can be 0.001 or more. The dielectric constant can be measured according to the method described in the embodiments below.

The cured product formed by heat curing the resin composition at 190°C for 90 minutes exhibits the property of low dielectric tangent. Therefore, the cured product has an insulating layer with low dielectric tangent. The dielectric tangent is preferably less than 0.01, more preferably less than 0.007, and even more preferably less than 0.005. The lower limit of the dielectric tangent may be greater than 0.0001, etc. The dielectric tangent may be measured according to the method described in the embodiments below.

The resin composition of the present invention can suppress the curing shrinkage rate and has an insulating layer with excellent dielectric constant. Therefore, the resin composition of the present invention is suitable for use as a resin composition for insulating purposes. Specifically, it is preferably used as a resin composition for forming an insulating layer (a resin composition for forming an insulating layer for forming a conductive layer) formed on the insulating layer (including a redistribution layer).

Furthermore, in the multilayer printed wiring board described later, it is preferably used as a 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), a 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 a resin composition for forming an insulating layer of a flexible substrate (resin composition for forming an insulating layer of a flexible substrate).

Furthermore, 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 applied as a resin composition for forming a redistribution layer (resin composition for forming a redistribution layer) of an insulating layer for forming a redistribution layer and a resin composition for sealing a semiconductor chip (resin composition for sealing a semiconductor chip). When manufacturing a semiconductor chip package, a redistribution layer can be further formed on the sealing layer. (1) a step of laminating a temporary fixing film on a substrate, (2) a step of temporarily fixing a semiconductor chip on the temporary fixing film, (3) a step of forming a sealing layer on the semiconductor chip, (4) a step of peeling the substrate and the temporary fixing film from the semiconductor chip, (5) a step of forming a redistribution layer as an insulating layer on the surface of the semiconductor chip from which the substrate and the temporary fixing film have been peeled, and (6) a step of forming a redistribution layer as a conductive layer on the redistribution layer

[Resin sheet] The resin sheet of the present invention comprises a support and a resin composition layer formed by the resin composition of the present invention disposed on the support.

The thickness of the resin composition layer is preferably 50 μm or less, more preferably 40 μm or less, and even more preferably 30 μm or less, from the viewpoint of providing a cured product having excellent insulation properties even when the printed wiring board is thinned and the cured product of the resin composition is a thin film. The lower limit of the thickness of the resin composition layer is not particularly limited, and it can usually be 5 μm or more.

As for the support, there can be mentioned, for example, a film made of a plastic material, a metal foil, and a release paper, with a film made of a plastic material and a metal foil being preferred.

When a film made of a plastic material is used as a support, the plastic material may include polyesters such as polyethylene terephthalate (hereinafter referred to as "PET"), polyethylene naphthalate (hereinafter referred to as "PEN"), polycarbonate (hereinafter referred to as "PC"), acrylic esters such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

When a metal foil is used as a support, the metal foil may be, for example, copper foil, aluminum foil, etc., with copper foil being preferred. The copper foil may be a foil made of copper alone, or a foil made of an alloy of copper and other metals (such as tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.).

The surface of the support system that is bonded to the resin composition layer may be subjected to matte treatment, corona treatment, and antistatic treatment.

In addition, the support may be a release layer-attached support having a release layer on the surface bonded to the resin composition layer. As the release agent used for the release layer of the release layer-attached support, for example, one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins and silicone resins may be mentioned. The support to which the release layer is attached may be a commercially available product, for example, a PET film having a release layer having an alkyd resin-based release agent as a main component, such as "SK-1", "AL-5", and "AL-7" manufactured by LINTEC, "Lumirror T60" manufactured by Toray, "Purex" manufactured by Teijin, and "unipeel" 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 in the range of 10 μm to 60 μm. In addition, when a support of a release layer is used, the thickness of the entire support of the release layer is preferably in the above range.

One embodiment is a resin sheet, which may include any layer as required. The arbitrary layer may be, for example, a protective film that is provided on the surface of the resin composition layer that is not bonded to the support (i.e., the surface opposite to the support) and is in contact with the support. The thickness of the protective film is not particularly limited, for example, 1 μm to 40 μm. By laminating the protective film, the adhesion or scratching of dust or the like on the surface of the resin composition layer can be suppressed.

The resin sheet can be produced, for example, by dissolving a resin composition in an organic solvent to prepare a resin paint, applying the resin paint on a support using a die coater or the like, and further drying the resin composition layer.

As for the organic solvent, there can be mentioned ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone; acetates such as ethyl acetate, butyl acetate, celulose acetate, propylene glycol monomethyl ether acetate and carbitol acetate; carbitols such as celulose and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone, etc. The organic solvent may be used alone or in combination of two or more.

Drying can be carried out by a well-known method such as heating or blowing hot air. The drying conditions are not particularly limited, and the resin composition layer is dried in such a manner that the content of the organic solvent is 10% by mass or less, preferably 5% by mass or less. Although it depends on the boiling point of the organic solvent in the resin coating, for example, when a resin coating containing 30% to 60% by mass of an organic solvent is used, the resin composition layer can be formed by drying it at 50°C to 150°C for 3 minutes to 10 minutes.

The resin sheet can be stored by rolling it into a roll. If the resin sheet has a protective film, the protective film can be peeled off before use.

[Printed wiring board] The printed wiring board of the present invention comprises an insulating layer formed by a cured product of the resin composition of the present invention.

A printed wiring board can be produced, for example, by using the above-mentioned resin sheet and then comprising the following steps (I) and (II). (I) A step of laminating the resin composition layer of the resin sheet on the inner substrate in such a manner as to bond the resin composition layer to the inner substrate (II) A step of thermally curing the resin composition layer to form an insulating layer

The "inner layer substrate" used in step (I) is a component that becomes the substrate of the printed wiring board, and examples thereof include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, etc. Furthermore, the substrate may have a conductive layer on one or both sides thereof, and the conductive layer may be patterned. An inner layer substrate having a conductive layer (circuit) formed on one or both sides of the substrate may be referred to as an "inner layer circuit substrate." Furthermore, during the manufacture of the printed wiring board, the intermediate product to be formed by the insulating layer and/or the conductive layer is further included in the "inner layer substrate" referred to in the present invention. When the printed wiring board is a circuit board with built-in components, an inner layer substrate with built-in components may be used.

The inner substrate and the resin sheet can be laminated, for example, by heat-pressing the resin sheet onto the inner substrate from the support body side. The member for heat-pressing the resin sheet onto the inner substrate (hereinafter referred to as the "heat-pressing member") can be, for example, a heated metal plate (SUS mirror plate, etc.) or a metal roller (SUS roller). In addition, the heat-pressing member is not directly pressed onto the resin sheet, but preferably, the resin sheet is pressed via an elastic material such as heat-resistant rubber in a manner that the resin sheet fully follows the surface irregularities of the inner substrate.

The lamination of the inner substrate and the resin sheet can be performed by vacuum lamination. In the vacuum lamination, the heating and pressing temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, the heating and pressing pressure is preferably in the range of 0.098MPa to 1.77MPa, more preferably in the range of 0.29MPa to 1.47MPa, and the heating and pressing time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. Lamination is preferably performed under reduced pressure conditions with a pressure of less than 26.7hPa.

Lamination can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressure laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum applicator manufactured by NIKKO Materials Co., Ltd., and a batch vacuum pressure laminator.

After lamination, the laminated resin sheet can be smoothed by, for example, applying pressure from the support side with a heat-pressing member under normal pressure (atmospheric pressure). The pressurizing conditions for the smoothing treatment can be the same as the heat-pressing conditions for the lamination described above. The smoothing treatment can be performed by a commercially available laminator. In addition, the lamination and smoothing treatment can also be performed continuously using the above-mentioned commercially available vacuum laminator.

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

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

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

Before the resin composition layer is heat-hardened, the resin composition layer may be preheated at a temperature lower than the hardening temperature. For example, before the resin composition layer is heat-hardened, the resin composition layer may be preheated at a temperature of 50°C to 120°C (preferably 60°C to 115°C, more preferably 70°C to 110°C) for more than 5 minutes (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and even more preferably 15 minutes to 100 minutes).

When manufacturing a printed wiring board, a step (III) of opening holes in the insulating layer, a step (IV) of roughening the insulating layer, and a step (V) of forming a conductive layer may be further performed. These steps (III) to (V) may be performed by various methods known to those skilled in the art in the art of manufacturing printed wiring boards. In addition, when the support is removed after step (II), the removal of the support may be performed between step (II) and step (III), between step (III) and step (IV), or between step (IV) and step (V). Furthermore, as required, the formation of the insulating layer and the conductive layer in steps (II) to (V) may be repeated to form a multi-layer wiring board.

Step (III) is a step of opening a hole in the insulating layer, thereby forming a through hole such as a via hole or a through hole in the insulating layer. Step (III) can also be implemented by using, for example, drilling, laser, plasma, etc., depending on the composition of the resin composition used in forming the insulating layer. The size or shape of the through hole can be appropriately determined according to the design of the printed wiring board.

Step (IV) is a step of roughening the insulating layer. Usually, stains are also removed in this step (IV). The procedure and conditions of the roughening treatment are not particularly limited, and the well-known procedures and conditions generally used when forming the insulating layer of the printed wiring board can be adopted. For example, the insulating layer is roughened by swelling treatment with a swelling liquid, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing liquid in sequence. The swelling liquid used in the roughening treatment is not particularly limited, and alkaline solutions, surfactant solutions, etc. can be cited. Alkaline solutions are preferred, and sodium hydroxide solutions and potassium hydroxide solutions are more preferred as the alkaline solutions. Examples of commercially available swelling liquids include "Swelling Dip Securiganth P", "Swelling Dip Securiganth SBU", and "Swelling Dip Securigant P" manufactured by Atotech Japan. The swelling treatment with the swelling liquid is not particularly limited, and for example, the swelling treatment can be performed by immersing the insulating layer in a swelling liquid at 30°C to 90°C for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate degree, it is preferred to immerse the insulating layer in a swelling liquid at 40°C to 80°C for 5 minutes to 15 minutes. There is no particular limitation on the oxidizing agent used in the roughening treatment, and an example thereof is an alkaline permanganic acid solution prepared by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. The roughening treatment using an oxidizing agent such as an alkaline permanganic acid solution is preferably carried out by immersing the insulating layer in the oxidizing agent solution heated to 60°C to 100°C for 10 minutes to 30 minutes. In addition, the concentration of permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. As for commercially available oxidizing agents, examples thereof include alkaline permanganic acid solutions such as "Concentrate Compact CP" and "Dosing solution Securiganth P" manufactured by Atotech Japan. In addition, the neutralizing solution used in the roughening treatment is preferably an acidic aqueous solution, and a commercially available product is, for example, "Reduction solution Securiganth P" manufactured by Atotech Japan. The treatment with the neutralizing solution can be carried out by immersing the surface treated by the roughening treatment with the oxidizing agent in the neutralizing solution at 30°C to 80°C for 1 minute to 30 minutes. From the perspective of workability, it is preferable to immerse the object treated by the roughening treatment with the oxidizing agent in the neutralizing solution at 40°C to 70°C for 5 minutes to 20 minutes.

In one embodiment, the arithmetic average roughness (Ra) of the insulating layer surface after the roughening treatment is preferably 300 nm or less, more preferably 250 nm or less, and even more preferably 200 nm or less. The lower limit is not particularly limited, but is preferably 30 nm or more, more preferably 40 nm or more, and even more preferably 50 nm or more. The arithmetic average roughness (Ra) of the insulating layer surface can be measured using a non-contact surface roughness meter.

Step (V) is a step of forming a conductive layer, and the conductive layer is formed on the insulating layer. The conductive material used in the conductive layer is not particularly limited. In a preferred embodiment, the conductive layer includes one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. The conductive layer can be a single metal layer or an alloy layer. As for the alloy layer, for example, a layer formed by an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy) can be mentioned. Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel-chromium alloy, copper-nickel alloy, or copper-titanium alloy is preferred; a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel-chromium alloy is more preferred; and a single metal layer of copper is more preferred.

The conductive layer may be a single layer structure or a multiple layer structure consisting of two or more single metal layers or alloy layers formed of different types of metals or alloys. When the conductive layer is a multiple layer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium or an alloy layer of nickel-chromium alloy.

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

In one embodiment, the conductive layer can be formed by plating. For example, by plating on the surface of the insulating layer by a well-known technique such as a semi-additive method or a full-additive method, a conductive layer having a desired wiring pattern can be formed. From the perspective of simplicity of manufacturing, it is preferably formed by a semi-additive method. The following shows an example of forming a conductive layer by a semi-additive method.

First, a coating seed layer is formed on the surface of the insulating layer by electroless plating. Then, a portion of the coating seed layer is exposed on the formed coating seed layer corresponding to the desired wiring pattern to form a mask pattern. After a metal layer is formed on the exposed coating seed layer by electrolytic plating, the mask pattern is removed. Thereafter, the unnecessary coating seed layer can be removed by etching or the like to form a conductor layer having the desired wiring pattern.

[Multi-layer flexible substrate] The multi-layer flexible substrate includes an insulating layer formed by a cured product of the resin composition of the present invention. The multi-layer flexible substrate may also include any component combined with the insulating layer. The arbitrary component may include, for example, electronic components, coating film, etc.

The multi-layer 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. Therefore, the multi-layer flexible substrate is manufactured by a manufacturing method including (a) the steps of preparing a resin sheet and (b) the steps of laminating and curing a plurality of resin composition layers using the resin sheet.

The method for manufacturing a multilayer flexible substrate can further combine any steps in the aforementioned steps. For example, the method for manufacturing a multilayer flexible substrate having electronic components can also include the step of bonding the electronic components to a laminated sheet. The bonding conditions between the laminated sheet and the electronic components can be any conditions that the terminal electrodes of the electronic components and the conductor layer of the wiring provided on the laminated sheet are conductively connected. Furthermore, for example, the method for manufacturing a multilayer flexible substrate having a coating film can include the step of laminating the laminated sheet and the coating film.

The multi-layer flexible substrate can be used by bending one side of the laminated sheet included in the multi-layer flexible substrate so that it faces each other. For example, the multi-layer flexible substrate can be stored in a housing of a semiconductor device in a state where the size is reduced by bending. In another example, the multi-layer flexible substrate can be installed in a movable part of a semiconductor device having a bendable movable part.

[Semiconductor device] The semiconductor device of the present invention includes the printed wiring board or multi-layer flexible substrate of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring board or multi-layer flexible substrate of the present invention.

As for semiconductor devices, there are various semiconductor devices provided to electrical products (e.g., computers, mobile phones, digital cameras, and televisions) and vehicles (e.g., motorcycles, automobiles, trains, ships, and aircrafts).

The semiconductor device of the present invention is manufactured by mounting a component (semiconductor chip) on the conductive part of a printed wiring board. The so-called "conductive part" is "the part that transmits the electrical signal in the printed wiring board", which can be the surface or buried. In addition, the semiconductor chip can be any electrical circuit element made of semiconductor as the material, and there is no particular limitation.

The semiconductor chip mounting method when manufacturing semiconductor devices is not particularly limited as long as the semiconductor chip can operate effectively. Specifically, there are wire bonding mounting methods, flip chip mounting methods, mounting methods using bumpless assembly layer (BBUL), mounting methods using anisotropic conductive film (ACF), and mounting methods using non-conductive film (NCF). Here, the so-called "mounting method using bumpless assembly layer (BBUL)" refers to "a mounting method in which a semiconductor chip is directly embedded in a recess of a printed wiring board to connect the semiconductor chip to the wiring on the printed wiring board." [Example]

Hereinafter, the present invention will be described in more detail with examples, but the present invention is not limited to these examples. In addition, in the following description, "parts" and "%" represent "parts by mass" and "% by mass" respectively, unless otherwise indicated.

<Synthesis Example 1: Synthesis of Polyimide Resin 1> In a 500 ml separable flask equipped with a nitrogen inlet and a stirring device, 9.13 g (30 mmol) of 5-aminobenzoic acid 1,1'-biphenyl-2-ester (compound of formula (B-3)), 4,4'-(4,4'-isopropyldiphenoxy) diphthalic acid, Anhydride 15.61g (30 mmol), N-methyl-2-pyrrolidone 94.64g, pyridine 0.47g (6 mmol), toluene 10g, and imidization reaction was carried out at 180°C under nitrogen atmosphere for 4 hours while observing toluene outside the system, to obtain a polyimide solution (non-volatile matter 20% by mass) containing polyimide resin 1. No precipitation of the synthesized polyimide resin 1 was observed in the polyimide solution. The weight average molecular weight of polyimide resin 1 was 45,000.

<Synthesis Example 2: Synthesis of Polyimide Resin 2> In a reaction vessel equipped with a stirrer, a water separator, a thermometer, and a nitrogen inlet tube, 65.0 g of aromatic tetracarboxylic dianhydride ("BisDA-1000" manufactured by SABIC JAPAN, 4,4'-(4,4'-isopropylidene diphenoxy) diphthalic dianhydride), 266.5 g of cyclohexanone, and 44.4 g of methylcyclohexane were placed, and the solution was heated to 60°C. Then, 43.7 g of dimerized diamine ("PRIAMINE 1075" manufactured by Croda Japan) and 5.4 g of 1,3-bis(aminomethyl)cyclohexane were dropped, and the imidization reaction was carried out at 140°C for 1 hour. Thus, a polyimide solution (non-volatile matter: 30% by mass) containing polyimide resin 2 was obtained. The weight average molecular weight of polyimide resin 2 was 25,000.

<Synthesis Example 3: Synthesis of Polyimide Resin 3> A 500 mL separable flask equipped with a water quantitative receiver connected to a circulating cooler, a nitrogen inlet tube and a stirrer was prepared. 20.3 g of 4,4'-oxydiphthalic anhydride (ODPA), 200 g of γ-butyrolactone, 20 g of toluene and 29.6 g of 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindane were added to the flask and stirred at 45°C for 2 hours under a nitrogen flow to react. Then, the reaction solution was heated to about 160°C while condensed water and toluene were removed azeotropically under a nitrogen flow. Confirm that a predetermined amount of water is accumulated in the water quantitative receiver and that no water is seen to flow out. After confirmation, the reaction solution is further heated and stirred at 200°C for 1 hour. Thereafter, it is cooled to obtain a polyimide solution (non-volatile matter 20% by mass) containing a polyimide resin 3 having a 1,1,3-trimethylindane skeleton. The obtained polyimide resin 3 has a repeating unit represented by the following formula (X1) and a repeating unit represented by the following formula (X2). In addition, the weight average molecular weight of the aforementioned polyimide resin 3 is 12,000.

<Synthesis Example 4: Synthesis of Compound A (Compound A) Containing an Aromatic Ester Skeleton and an Unsaturated Bond> 89 parts by mass of o-allylphenol, 110 parts by mass of dicyclopentadiene-phenol copolymer resin (softening point 85°C, hydroxyl equivalent of about 165 g/eq.), and 1000 parts by mass of toluene were placed in a reaction container, and the container was depressurized and nitrogen substituted while being dissolved. Next, 135 parts by mass of isophthalic acid chloride was placed and dissolved. Next, 0.5 g of tetrabutylammonium bromide was added, and 309 g of a 20% aqueous sodium hydroxide solution was dripped over 3 hours while the container was purged with nitrogen. At this time, the temperature in the system was controlled below 60°C. Thereafter, the reaction was stirred for 1 hour. After the reaction is completed, the reactants are separated and the aqueous layer is removed. This operation is repeated until the pH of the aqueous layer reaches 7, and toluene and the like are distilled off under heating and reduced pressure conditions to obtain a compound A containing an aromatic ester skeleton and unsaturated bonds. The unsaturated bond equivalent of the obtained compound A containing an aromatic ester skeleton and unsaturated bonds is 428 g/eq., if calculated by the insertion ratio. Compound A is represented by the following formula, s represents an integer greater than 0 or 1, and the average value of r calculated by the insertion ratio is 1. In addition, the wavy line is the structure obtained by the reaction of isophthalic acid chloride, and the heavy addition reaction resin of phenol and/or o-allylphenol.

<Synthesis Example 5: Synthesis of Compound B Containing an Aromatic Ester Skeleton and an Unsaturated Bond (Compound B)> Place 201 parts by mass of o-allylphenol and 1000 parts by mass of toluene in a reaction vessel, and dissolve them while reducing the pressure in the vessel to replace with nitrogen. Next, place 152 parts by mass of isophthalic acid chloride and dissolve it. While purging the inside of the container with nitrogen, drop 309 g of a 20% aqueous sodium hydroxide solution over 3 hours. At this time, the temperature in the system is controlled below 60°C. Thereafter, stir for 1 hour to react. After the reaction is completed, separate the reactants and remove the aqueous layer. Repeat this operation until the pH of the aqueous layer reaches 7, and distill off toluene and the like under heating and reduced pressure to obtain Compound B containing an aromatic ester skeleton and an unsaturated bond. The obtained compound B containing an aromatic ester skeleton and unsaturated bonds had an unsaturated bond equivalent of 199 g/eq. calculated from the insertion ratio. The compound B had a structure represented by the following formula.

<Example 1: Preparation of Resin Composition 1> 5 parts of bis(xylenol) epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185 g/eq.), 5 parts of naphthalene epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumitomo Chemical Corporation, epoxy equivalent of about 332 g/eq.), 5 parts of bisphenol AF epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185 g/eq.), and 1 part of bis(xylenol) epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumitomo Chemical Corporation, epoxy equivalent of about 332 g/eq.) were added. , epoxy equivalent of about 238 g/eq.), 10 parts of cyclohexane type epoxy resin ("ZX1658GS" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 135 g/eq.), 100 parts of polyimide resin 1 obtained in Synthesis Example 1 (non-volatile component 20 mass %) and 10 parts of cyclohexanone are stirred and dissolved in a mixed solvent under heating. After cooling to room temperature, 5 parts of the compound A obtained in Synthesis Example 4, 4 parts of a triazine skeleton-containing cresol novolac hardener ("LA3018-50P" manufactured by DIC Corporation, hydroxyl equivalent of about 151 g/eq., 2-methoxypropanol solution with a solid content of 50%), and spherical silica ("SC2500SQ" manufactured by Admatechs Corporation, average particle size of 0.5 μm, specific surface area of 11.2 ^m2) were added thereto. /g, 50 parts of N-phenyl-3-aminopropyltrimethoxysilane (KBM573, manufactured by Shin-Etsu Chemical Co., Ltd.) with respect to 100 parts of silicon oxide, 0.2 parts of an amine-based curing accelerator (4-dimethylaminopyridine (DMAP)) and 0.03 parts of a peroxide-based curing accelerator (PERBUTYL C, manufactured by NOF Corporation) were mixed, uniformly dispersed with a high-speed rotary mixer, and filtered with a cartridge filter (SHP020, manufactured by ROKITECHNO Co., Ltd.) to prepare a resin composition 1.

<Example 2: Preparation of Resin Composition 2> In Example 1, 5 parts of Compound A were replaced with 10 parts of Compound B (non-volatile component 50% by mass). Except for the above matters, the rest was implemented in the same way as Example 1 to prepare Resin Composition 2.

<Example 3: Preparation of Resin Composition 3> In Example 1, 100 parts of polyimide resin 1 (non-volatile component 20 mass%) obtained in Synthesis Example 1 were replaced with 66.7 parts of polyimide resin 2 (non-volatile component 30 mass%) obtained in Synthesis Example 2. Except for the above matters, the rest was implemented in the same way as in Example 1 to prepare resin composition 3.

<Example 4: Preparation of Resin Composition 4> In Example 1, 100 parts of polyimide resin 1 (non-volatile component 20 mass%) obtained in Synthesis Example 1 were replaced with 100 parts of polyimide resin 3 (non-volatile component 20 mass%) obtained in Synthesis Example 3. Except for the above matters, the rest was implemented in the same way as Example 1 to prepare resin composition 4.

<Comparative Example 1: Preparation of Resin Composition 5> In Example 1, 5 parts of Compound A obtained in Synthesis Example 4 were replaced with 7.7 parts of an active ester hardener ("EXB-8000L-65TM" manufactured by DIC Corporation, with an active group equivalent of about 220 g/eq., and a 1:1 solution of toluene:MEK containing 65% by mass of non-volatile components). Except for the above matters, the rest was carried out in the same manner as in Example 1 to prepare Resin Composition 5.

<Comparative Example 2: Preparation of Resin Composition 6> In Example 1, 5 parts of Compound A obtained in Synthesis Example 4 were replaced with 8.1 parts of an active ester-based curing agent ("EXB-8150-62T" manufactured by DIC Corporation, with an active group equivalent of about 230 g/eq. and a toluene solution containing 62% non-volatile components by mass). Except for the above matters, the rest was carried out in the same manner as in Example 1 to prepare Resin Composition 6.

<Measurement of average particle size of inorganic filler> 100 mg of inorganic filler and 10 g of methyl ethyl ketone were weighed in a small glass bottle and dispersed by ultrasound for 10 minutes. The particle size distribution of the inorganic filler was measured on a volume basis using a laser diffraction particle size distribution measuring device ("LA-960" manufactured by Horiba, Ltd.) with the wavelength of the light source adjusted to blue and red. The average particle size of the inorganic filler was calculated as the median diameter from the obtained particle size distribution.

<Measurement of specific surface area of inorganic filler> The specific surface area of the inorganic filler was measured by using a BET fully automatic specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) to adsorb nitrogen on the sample surface and calculate the specific surface area using the BET multipoint method.

<Determination of Curing Shrinkage> (1-1) Preparation of Resin Sheet The resin composition of each embodiment and comparative example was uniformly coated on the release-treated surface of a PET film (thickness 38 μm) treated with an alkyd release agent using a die coater so that the thickness of the resin composition layer after drying was 40 μm. The film was dried at 80-120°C (average 100°C) for 6 minutes to obtain a resin sheet 1.

(1-2) Preparation of a resin-attached polyimide film After processing the resin sheet 1 into a 200 mm angle, a batch vacuum pressure laminator (manufactured by Nichigo-Morton, 2-platform assembly laminator, CVP700) was used to laminate on one side in such a way that the resin composition layer was in contact with the center of the smooth surface of a polyimide film (manufactured by Ube Industries, Ltd., UPILEX 25S, 25 μm thick, 240 mm angle), thereby obtaining a resin-attached polyimide film. Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressing the film at 100°C and a pressure of 0.74 MPa for 30 seconds.

(1-3) Measurement of initial length The obtained resin-attached polyimide film was punched through with holes (about 6 mm in diameter) at about 20 mm from the four corners of the 200 mm angular resin on the support of the resin sheet to form four holes (the holes are temporarily referred to as A, B, C, and D in chronological order). After the support of the resin sheet was peeled off, the center-to-center length L (L _AB , L BC , L CD , L DA , _{L AC} , and L _BD ) of each hole formed was measured using a non-contact image measuring device ( _{MITUTOYO Co.} , Ltd., Quick Vision model: QVH1X606-PRO _{III_BHU2G} ) (see FIG1 ). In addition, in FIG. 1 , X and Y represent the longitudinal direction and the transverse direction of the resin sheet.

(1-4) Thermal curing of the resin composition layer After the length measurement, the resin-attached polyimide film was placed on a 255 mm × 255 mm glass cloth-based epoxy resin laminate (0.7 mm thick, "R5715ES" manufactured by Matsushita Electric Works Co., Ltd.), and the four sides were fixed with polyimide adhesive tape (10 mm wide). The resin composition layer was thermally cured by heating at 190°C for 90 minutes to obtain a cured layer.

(1-5) Determination of thermal curing shrinkage rate After thermal curing, the polyimide adhesive tape is peeled off, and the polyimide film with the cured material layer is removed from the laminate. The cured material layer is further peeled off from the polyimide film, and the length L'(L' _AB , L' _BC , L' _CD , L' _DA , L' _AC , L' _BD ) between the centers of each hole formed in (1-3) after curing is measured using a non-contact image measuring device in the same manner as L.

The length L _AB between holes A and B is obtained by the following formula (1) and its shrinkage rate s1 _AB after curing. Similarly, the shrinkage rates s1 _BC , s1 _CD , s1 _DA , s1 _AC and s1 _DA of L _BC , L _CD , L _DA , L _AC and L _BD after curing are obtained. s1 _AB =(L _AB -L' _AB )/L _AB (1)

The hardening shrinkage rate of the hardened layer is obtained by the following formula (2). Hardening shrinkage rate [shrinkage rate in the xy direction: S1] (%) = {(s1 _AB +s1 _BC +s1 _CD +s1 _DA +s1 _AC +s1 _DA )/6} × 100 (2)

In addition, the hardening shrinkage rate of the hardened layer is evaluated according to the following criteria. ○: Hardening shrinkage rate is 0.35% or less ×: Hardening shrinkage rate exceeds 0.35%

<Measurement of dielectric properties (dielectric constant, dielectric tangent)> The resin sheet 1 prepared in (1-1) was laminated on a laminate plate (copper foil etched product of MCL-E-700G manufactured by Hitachi Chemical Co., Ltd.) using a batch vacuum pressure laminator ("MVLP-500" manufactured by Meiki Seisakusho Co., Ltd.). The laminate was decompressed for 30 seconds to a pressure of 13 hPa or less, and then pressed at 120°C for 30 seconds and a pressure of 0.74 MPa. Thereafter, the PET film was peeled off, and the resin composition layer was cured under the curing conditions of 190°C for 90 minutes to obtain a cured sample.

The hardened sample was cut into test pieces with a width of 2 mm and a length of 80 mm. For the test piece, the "HP8362B" manufactured by Agilent Technologies was used to measure the dielectric constant and dielectric tangent by the cavity resonance perturbation method at a frequency of 5.8 GHz and a temperature of 23°C. The three test pieces were measured and the average value was calculated. In addition, the dielectric constant was evaluated based on the following criteria. ○: Dielectric constant is less than 3.0 ×: Dielectric constant exceeds 3.0

* In the table, "content of component (A)" indicates the content of component (A) when the non-volatile components in the resin composition are 100 mass %, "content of component (B)" indicates the content of component (B) when the non-volatile components in the resin composition are 100 mass %, and "content of component (C)" indicates the content of component (C) when the non-volatile components in the resin composition are 100 mass %.

It has been confirmed that in Examples 1 to 4, even when the components (C) to (E) are not contained, the results are the same as those of the above-mentioned Examples, although the degree of difference is different.

[Fig. 1] Fig. 1 is a schematic diagram showing an example of a resin sheet when measuring the curing shrinkage rate.

Claims (11)

A resin composition for forming an insulating layer, which is a resin composition containing the following components: (A) a compound containing an aromatic ester skeleton and having a substituent selected from an alkenyl group having 2 to 30 carbon atoms and an alkynyl group having 2 to 30 carbon atoms, (B) a polyimide resin, (C) silicon oxide, and (D) an epoxy resin; when the non-volatile component in the resin composition is 100% by mass, the content of the component (B) is 10% by mass or more and 50% by mass or less. A resin composition comprising the following components: (A) a compound containing an aromatic ester skeleton and an unsaturated bond, (B) a polyimide resin, (C) silicon oxide, and (D) an epoxy resin; component (A) is any one of a compound represented by the following general formula (A-1) and a compound represented by the following general formula (A-2), and when the non-volatile component in the resin composition is 100% by mass, the content of component (B) is 10% by mass or more and 50% by mass or less,

(In general formula (A-1), Ar ¹¹ each independently represents a monovalent aromatic hydrocarbon group which may have a substituent, Ar ¹² each independently represents a divalent aromatic hydrocarbon group which may have a substituent, Ar ¹³ each independently represents a divalent aromatic hydrocarbon group which may have a substituent, a divalent aliphatic hydrocarbon group which may have 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, and at least one aromatic hydrocarbon group contained in general formula (A-1) has a substituent having at least one unsaturated bond);

(In general formula (A-2), Ar ²¹ represents an m-valent aromatic hydrocarbon group which may have a substituent, Ar ²² each independently represents a monovalent aromatic hydrocarbon group which may have a substituent, m represents an integer of 2 or 3, and at least one aromatic hydrocarbon group contained in general formula (A-2) has a substituent containing at least one unsaturated bond). The resin composition of claim 1 or 2, wherein the content of component (A) is 0.1% by mass or more and 30% by mass or less, when the non-volatile components in the resin composition are 100% by mass. The resin composition of claim 1 or 2, wherein the content of component (C) is 30% by mass or more when the non-volatile components in the resin composition are 100% by mass. The resin composition in claim 2 is used to form an insulating layer. The resin composition of claim 1 or 2 is used to form an insulating layer of a conductive layer. A resin sheet comprising a support and a resin composition layer disposed on the support containing a resin composition as described in any one of claims 1 to 6. A printed wiring board comprising an insulating layer formed by a cured product of a resin composition as described in any one of claims 1 to 6. A multi-layer flexible substrate comprising an insulating layer formed by curing a resin composition as described in any one of claims 1 to 6. A semiconductor device comprising a printed wiring board as claimed in claim 8. A semiconductor device comprising a multi-layer flexible substrate as claimed in claim 9.

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