Curable composition, cured product, and method for forming an insulating film

Abstract

The present invention provides a curable composition capable of forming a cured product having low dielectric constant and dielectric loss tangent, excellent heat resistance, elongation and tensile strength, and excellent film-forming properties, a cured product of the said curable composition, and a method for forming an insulating film using the said curable composition. A maleimide modified compound (A), a radical generator (C), and a thiol compound (D) are combined in a curable composition. It is preferable that the curable composition includes a photoradical generator (C1) as the radical generator (C). Additionally, it is preferable that the curable composition includes a protic acid (E).

Description

Technology Field

[0001] The present invention relates to a curable composition, a cured product, and a method for forming an insulating film. Background Technology

[0002] Recently, communication devices such as mobile phones are becoming more high-frequency. Consequently, insulating films that insulate the metal wiring of these devices are also required to cope with high frequencies.

[0003] Here, transmission loss increases as the frequency increases, and as transmission loss increases, the electrical signal attenuates. Therefore, as a countermeasure to high frequency, it is required to reduce transmission loss.

[0004] In order to reduce transmission loss, a technique for forming an insulating film using a material with low dielectric constant and dielectric loss tangent is disclosed (e.g., Patent Document 1). Prior art literature

[0005] Japanese Published Patent Application No. 2004-87639 The problem to be solved

[0006] However, the technology of Patent Document 1 is a technology that uses a resin composition of a specific structure, specifically a resin composition containing a crosslinking component represented by Formula (1) described in Patent Document 1. For this reason, there is a need for a technology that uses a composition other than the composition described in Patent Document 1.

[0007] Furthermore, the same requirement for high frequency response is also applied to electrical and electronic devices other than communication equipment, such as network-related electronic devices like servers and electronic devices like computers.

[0008] Furthermore, in the manufacture of electrical and electronic devices, it is common for an insulating film to be formed from a composition, followed by heating and the subsequent formation of components such as wiring. For this reason, heat resistance is also required for the insulating film.

[0009] When forming an insulating film from a composition, the insulating film can be easily formed by a coating method. For this reason, it is desirable that the composition be applicable to a coating method, that is, that it has excellent film-forming properties in a coating method.

[0010] Furthermore, as exemplified by applications such as panels for flexible display devices, there is an increasing demand for insulating films to have durability against deformation, such as elongation. For this reason, regarding compositions capable of forming insulating films, there is a demand for films with excellent elongation and tensile strength.

[0011] The present invention, made in consideration of the above problem, aims to provide a curable composition capable of forming a cured product having low dielectric constant and dielectric loss tangent, excellent heat resistance, elongation and tensile strength, and excellent film-forming properties, a cured product of said curable composition, and a method for forming an insulating film using said curable composition. means of solving the problem

[0012] The inventors have discovered that a curable composition comprising a radical generator (C) and a thiol compound (D), together with a maleimide modified compound (A) having a radical polymerizable group of a specific structure including a maleimide backbone, provides a cured product with low dielectric constant and dielectric loss tangent, excellent heat resistance, elongation and tensile strength, and also excellent film-forming properties, thereby completing the present invention.

[0013] A first aspect of the present invention comprises a maleimide modified compound (A), a radical generator (C), and a thiol compound (D), and

[0014] Maleimide modified compound (A) is, formula (a1) below:

[0015] [Chemical Formula 1]

[0016]

[0017] Having one or more units represented by,

[0018] A group represented by formula (a1) is bonded to a carbon atom in an aliphatic hydrocarbon group or an aromatic group in a maleimide modified compound (A), and

[0019] In equation (a1), R a01 and R a02 Each is a curable composition that is independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms.

[0020] A second aspect of the present invention is a cured product of a curable composition related to the first aspect.

[0021] A third aspect of the present invention comprises a coating process for forming a coating film by applying a curable composition related to the first aspect to an insulating film formation site, and

[0022] It is a method for forming an insulating film, comprising a curing process for curing a coating film. Effects of the invention

[0023] According to the present invention, a curable composition having low dielectric constant and dielectric loss tangent, excellent heat resistance, elongation and tensile strength, and excellent film-forming properties can be provided, a cured product of said curable composition, and a method for forming an insulating film using said curable composition. Specific details for implementing the invention

[0024] Curable composition

[0025] The curable composition comprises a maleimide modified compound (A), a radical generator (C), and a thiol compound (D).

[0026] The maleimide modified compound (A) is of the following formula (a1):

[0027] [Chemical Formula 2]

[0028]

[0029] It has one or more groups represented by. The group represented by formula (a1) is bonded to a carbon atom in an aliphatic hydrocarbon group or an aromatic group in the maleimide modified compound (A).

[0030] In equation (a1), R a01 and R a02 a, each independently, is a hydrogen atom, an alkyl group with 1 to 6 carbon atoms, a cycloalkyl group with 3 to 8 carbon atoms, or an aryl group with 6 to 12 carbon atoms.

[0031] The curable composition comprising the above maleimide modified compound (A) and the radical generator (C) provides a cured product having good film-forming properties, low dielectric constant and dielectric loss tangent, and excellent heat resistance.

[0032] By including a thiol compound (D) together with a maleimide modified compound (A), a curable composition can be used to form a cured product with excellent elongation and tensile strength.

[0033] The curable composition is preferably used to form an insulating film. Typically, the curable composition is used to form an insulating film that insulates the metal wiring in an electrical or electronic device having metal wiring.

[0034] Electrical and electronic devices are not particularly limited and include communication devices such as mobile phones, network-related electronic devices such as servers, and electronic devices such as computers, in particular, semiconductor components of these devices, specifically semiconductor packages referred to as wafer-level packages.

[0035] These electrical and electronic devices have metal wiring made of metals or alloys, such as copper, on a substrate for electrical and electronic devices. Examples of substrates for electrical and electronic devices having metal wiring include silicon substrates or substrates on which various layers or components are formed.

[0036] This metal wiring and other metal wiring or conductive members are insulated by an insulating film formed by a curable composition.

[0037] By using a curable composition containing the components described below, an insulating film with low dielectric constant and dielectric loss tangent (tanδ) can be formed. For this reason, a curable composition containing the components described below is preferred for insulating films that insulate metal wiring of electrical and electronic devices using high-frequency signals. Furthermore, in this specification, "high frequency" means a frequency of 3 GHz or higher.

[0038] In addition, since it can form an insulating film with excellent heat resistance, the curable composition can be used, for example, to form an insulating film in an electrical or electronic device in which another component is formed by heating after the insulating film is formed by the curable composition.

[0039] In addition, the curable composition imparts a cured product with excellent elongation and tensile strength. For this reason, an insulating film formed using the curable composition can be preferably used in applications where bending stress or tensile stress is applied, such as panels for flexible display devices.

[0040] The curable composition has excellent film-forming properties in the coating method, that is, when formed by the coating method, there is no occurrence of cracks or crystals, no tack (stickiness), and good compatibility of components, so an insulating film can be formed by the coating method, which is an easy method.

[0041] The following describes the essential or optional components included in the curable composition.

[0042] <Maleimide modified compound (A)>

[0043] The curable composition contains a maleimide modified compound (A) having one or more groups represented by the following formula (a1) in one molecule. The group represented by the following formula (a1) is bonded to a carbon atom in an aliphatic hydrocarbon group or an aromatic group included in the maleimide modified compound (A). The maleimide modified compound (A) may be a maleimide modified resin (A1) which is a polymer having one or more groups represented by the following formula (a1) in one molecule, or a maleimide monomer (A2) which is a nonpolymer having one or more groups represented by the following formula (a1) in one molecule. In terms of forming a cured product with excellent mechanical properties, heat resistance, chemical resistance, etc., the maleimide modified compound (A) is preferably composed only of a maleimide modified resin (A1) or a combination of a maleimide modified resin (A1) and a maleimide modified monomer (A2).

[0044] [Chemical Formula 3]

[0045]

[0046] (In equation (a1), R a01 and R a02 Each is independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms.

[0047] R in equation (a1) a01 and R a02 The alkyl group having 1 to 6 carbon atoms as a group may be a straight-chain alkyl group or a branched-chain alkyl group. Specific examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, and an isohexyl group.

[0048] R in equation (a1) a01 and R a02Specific examples of cycloalkyl groups having 3 to 8 carbon atoms include cyclopropyl groups, cyclobutyl groups, cyclopentyl groups, and cyclohexyl groups.

[0049] R in equation (a1) a01 and R a02 Specific examples of aryl groups having 6 or more and 12 or fewer carbon atoms include phenyl groups, biphenyl groups, 1-naphthyl groups, and 2-naphthyl groups.

[0050] R in equation (a1) a01 and R a02 It is desirable that they are all hydrogen atoms. R a01 and R a02 If all atoms are hydrogen atoms, the maleimide modified compound (A) has excellent polymerization properties. For this reason, it is easy to obtain a curable composition with excellent curability. R a01 and R a02 In the case where all atoms are hydrogen atoms, the group represented by formula (a1) becomes an unsubstituted maleimide group.

[0051] The bonding position of the group represented by formula (a1) in the maleimide modified compound (A) is not particularly limited to the extent that it does not impede the purpose of the present invention. When the maleimide modified compound (A) is a maleimide modified resin (A1), it is preferable that the group represented by formula (a1) in the maleimide modified resin (A1) is bonded to a carbon atom located other than the end of the main chain of the maleimide modified resin (A1), as a carbon atom in an aliphatic hydrocarbon group or an aromatic group in the main chain and / or side chain of the maleimide modified resin (A1). That is, it is preferable that the maleimide modified resin (A1) has a structure in which a hydrogen atom bonded to a carbon atom located other than the end of the main chain of the maleimide modified resin (A1), which is a carbon atom in an aliphatic hydrocarbon group or an aromatic group in the main chain and / or side chain of the resin, is substituted with a group represented by formula (a1).

[0052] Examples of resins that impart a maleimide-modified resin (A1) of such a structure include polymers of monomers having unsaturated double bonds. Examples of such resins include (meth)acrylic resins or polystyrene-based resins. In addition, in this specification, "(meth)acrylic" means both "acrylic" and "methacrylic".

[0053] "(Meth)acrylic resin" is a resin comprising a constituent unit derived from one or more monomers selected from the group consisting of (meth)acrylic acid, (meth)acrylic acid esters, and (meth)acrylamides that may be N-substituted. The (meth)acrylic resin may also comprise a constituent unit derived from monomers other than (meth)acrylic acid, (meth)acrylic acid esters, and (meth)acrylamides that may be N-substituted.

[0054] "Polystyrene-based resin" is a resin containing constituent units derived from styrene and / or styrene derivatives.

[0055] In the specification of this application, a resin comprising a constituent unit derived from one or more monomers selected from the group consisting of (meth)acrylic acid, (meth)acrylic acid esters, and (meth)acrylamides which may be N-substituted, and a constituent unit derived from styrene and / or styrene derivatives is conveniently treated as a (meth)acrylic resin.

[0056] In addition, in this specification, "side chain" means a molecular chain branching from the main chain. For example, if the resin is a (meth)acrylic resin, a carboxyl group, an ester group, an N-substituted amide group, or a methyl group bonded to the α-carbon of the (meth)acrylic resin monomer is a side chain. If the resin is a styrene-based resin, a phenyl group bonded to a carbon atom derived from a carbon-carbon double bond of the styrene-based resin monomer, or a derivative thereof, is a side chain.

[0057] In the maleimide modified resin (A1), the group represented by formula (a1) is bonded to a carbon atom located outside the end of the main chain of the maleimide modified resin (A1) as a carbon atom in the aliphatic hydrocarbon group or an aromatic group in the main chain and / or side chain of the maleimide modified resin (A1), so the group represented by formula (a1) is at least part of the side chain of the maleimide modified resin (A1).

[0058] For example, in the case where a group represented by the formula (a1) is bonded to a carbon atom located outside the end of the main chain of the maleimide modified resin (A1) as a carbon atom in the aliphatic hydrocarbon group or an aromatic group in the main chain of the maleimide modified resin (A1), the maleimide modified resin (A1) has a structure having an aliphatic hydrocarbon group or an aromatic group in the main chain, and a group represented by the formula (a1) is bonded to a carbon atom in the aliphatic hydrocarbon group or an aromatic group in the main chain. For this reason, the group represented by the formula (a1) corresponds to a side chain of the maleimide modified resin (A1).

[0059] In the case where a group represented by the formula (a1) is bonded to a carbon atom in an aliphatic hydrocarbon group or an aromatic group in a side chain of the maleimide modified resin (A1), the maleimide modified resin (A1) has a structure having an aliphatic hydrocarbon group or an aromatic group in a side chain, and a group represented by the formula (a1) is bonded to a carbon atom in an aliphatic hydrocarbon group or an aromatic group in this side chain. For this reason, the group represented by the formula (a1) corresponds to a part of the side chain of the maleimide modified resin (A1).

[0060] In the maleimide modified resin (A1), the carbon atom in the main chain and / or side chain of the maleimide modified resin (A1) that is an aliphatic hydrocarbon group or an aromatic group may be bonded to a carbon atom located other than the end of the main chain of the maleimide modified resin (A1), and the group represented by the above formula (a1) may be bonded to it. Additionally, the carbon atom located at the end of the main chain of the maleimide modified resin (A1) may be bonded to a group represented by the above formula (a1).

[0061] It is preferable that the group represented by formula (a1) be included in the constituent unit of the resin.

[0062] The main chain of the maleimide modified resin (A1) is not limited to these, but is preferably, for example, a main chain derived from (meth)acrylic resin or a main chain derived from polystyrene-based resin. (Meth)acrylic resin or polystyrene-based resin has low dielectric constant and dielectric loss tangent. For this reason, if the main chain is a main chain derived from (meth)acrylic resin or a main chain derived from polystyrene-based resin, the dielectric constant and dielectric loss tangent of the formed insulating part can be further reduced.

[0063] The molecular weight of the maleimide modified resin (A1) is not particularly limited as long as it does not impede the effects of the present invention. The mass average molecular weight (Mw) is preferably 4,000 or more, more preferably 5,000 or more, and even more preferably 10,000 or more. The molecular weight of the maleimide modified resin (A1) is preferably 100,000 or less as the mass average molecular weight (Mw), and more preferably 80,000 or less.

[0064] In this specification, the mass average molecular weight (Mw) is a measurement obtained by the polystyrene conversion of gel permeation chromatography (GPC).

[0065] The method for preparing the maleimide modified compound (A) is not particularly limited. Specifically, the maleimide modified compound (A) comprises a primary amino group in a raw material compound, such as a resin having a primary amino group and the following formula (a2):

[0066] [Chemical Formula 4]

[0067]

[0068] (In equation (a2), R a01 and R a02 is R in equation (a1) a01 and R a02 Identical to,

[0069] R a1 ~ R a6 Each is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and R a1 and R a5 ...combined with each other, -O-, -S-, -CH2-, or -CR a7 R a8 - It may form, and R a3 and R a4 They may combine with each other to form a ring with 6 to 12 carbon atoms, and

[0070] R a7 and R a8 Each is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

[0071] By condensing the dicarboxylic acid anhydride represented by, the following formula (a3):

[0072] [Chemical Formula 5]

[0073]

[0074] (Equation (a3), R a01 and R a02 is R in equation (a1) a01 and R a02 Same as, and Ra1 ~ R a6 is R in equation (a2) a1 ~ R a6 It is identical to.)

[0075] A first process for generating a gas represented by, and

[0076] It can be manufactured by a manufacturing method comprising a second process of heating an intermediate compound having a group represented by formula (a3) ​​generated in a first process to convert the group represented by formula (a3) ​​into a group represented by formula (a1).

[0077] R in equation (a2) a1 ~ R a6 Specific examples of halogen atoms include chlorine atoms, fluorine atoms, bromine atoms, and iodine atoms.

[0078] R in equation (a2) a1 ~ R a6 The alkyl group having 1 to 4 carbon atoms as a group may be a straight-chain alkyl group or a branched-chain alkyl group. Specific examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.

[0079] R in equation (a2) a1 ~ R a6 The alkoxy group having 1 to 4 carbon atoms as a group may be a straight-chain alkoxy group or a branched-chain alkoxy group. Specific examples include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, and an n-butoxy group.

[0080] R a7 and R a8 The alkyl group having 1 to 4 carbon atoms and the alkoxy group having 1 to 4 carbon atoms as R a1 ~ R a6 It is identical to an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms.

[0081] In the first process, the primary amino group in a raw material compound having a primary amino group is condensed with a dicarboxylic acid anhydride represented by formula (a2) to produce a group represented by formula (a3). By doing so, a resin having a group represented by formula (a3) ​​is obtained.

[0082] Examples of raw material compounds having a primary amino group include polymers of monomers having unsaturated double bonds. Examples of such resins include (meth)acrylic resins having a primary amino group or polystyrene-based resins having a primary amino group. More specific examples include (meth)acrylic resins having a primary amino group at the end of a side chain or polystyrene-based resins having a primary amino group at the end of a side chain.

[0083] "(Meth)acrylic resin having a primary amino group" is a (meth)acrylic resin comprising a constituent unit having a primary amino group. The constituent unit having a primary amino group may be a constituent unit derived from a (meth)acrylic acid ester, a constituent unit derived from an N substituent of (meth)acrylamide, or a constituent unit other than these constituent units. It is preferable that the constituent unit having a primary amino group is a constituent unit derived from a (meth)acrylic acid ester and / or a constituent unit derived from an N substituent of (meth)acrylamide.

[0084] "Polystyrene-based resin having a primary amino group" is a polystyrene-based resin comprising a constituent unit having a primary amino group. The constituent unit having a primary amino group may be a constituent unit derived from aminostyrene such as p-aminostyrene, m-aminostyrene, and o-aminostyrene, a constituent unit derived from styrene derivatives having an amino group such as p-aminomethylstyrene, m-aminomethylstyrene, and o-aminomethylstyrene, or a constituent unit other than these constituent units. It is preferable that the constituent unit having a primary amino group is a constituent unit derived from aminostyrene and / or a constituent unit derived from a styrene derivative having an amino group.

[0085] It is preferable that a resin having a primary amino group, such as a (meth)acrylic resin having a primary amino group or a polystyrene-based resin having a primary amino group, has a primary amino group at the end of the side chain.

[0086] In the case of a (meth)acrylic resin having a primary amino group at the end of a side chain or a polystyrene-based resin having a primary amino group at the end of a side chain, if the side chain is a branched chain, the end of the side chain to which the primary amino group is attached may be any of the two or more ends of the branched chain. Also, if the structure of the end of the side chain is a ring structure, any position of the ring constituting the ring structure is the end of the side chain to which the primary amino group is attached.

[0087] For example, if the side chain consists of an α-naphthyl group or a β-naphthyl group, any position on the naphthalene ring is the end of the side chain. Also, if the group constituting the side chain is a branched chain type 1-phenylethyl group, any position on the methyl group and the phenyl group corresponding to the ends of the two branched chains is the end of the side chain.

[0088] In a method for manufacturing a maleimide modified resin (A1), the resin (raw material compound) having a primary amino group is preferably produced by homopolymerizing a monomer having a primary amino group to produce a raw material compound that is a resin, or by copolymerizing a monomer having a primary amino group with a comonomer to produce a raw material compound that is a resin.

[0089] Monomers having a primary amino group include (meth)acrylates such as aminomethyl(meth)acrylate, 2-aminoethyl(meth)acrylate, 3-aminopropyl(meth)acrylate, 4-aminophenyl(meth)acrylate, 3-aminophenyl(meth)acrylate, 2-aminophenyl(meth)acrylate, 4-aminophenylmethyl(meth)acrylate, 3-aminophenylmethyl(meth)acrylate, and 2-aminophenylmethyl(meth)acrylate; (meth)acrylamides such as N-2-aminoethyl(meth)acrylamide, N-3-aminopropyl(meth)acrylamide, N-4-aminophenyl(meth)acrylamide, N-3-aminophenyl(meth)acrylamide, and N-2-aminophenyl(meth)acrylamide; and aminostyrenes such as p-aminostyrene, m-aminostyrene, and o-aminostyrene; Examples include aminoalkylstyrenes such as p-aminomethylstyrene, m-aminomethylstyrene, and o-aminomethylstyrene.

[0090] A comonomer is a monomer other than a monomer having a primary amino group. Examples of comonomers include compounds represented by the following formula (aI).

[0091] CH2=CR a11 -CO-OR a10 ··· (aI)

[0092] In equation (aI), R a10 Silver, organic contribution of 1, R a11It is a hydrogen atom or a methyl group. An organic group includes a hydrocarbon group, and the hydrocarbon group may be an aliphatic hydrocarbon or an aromatic hydrocarbon. The structure of the aliphatic hydrocarbon group may be a straight chain, a branched chain, a ring, or a combination thereof. This organic group may include bonds or substituents other than hydrocarbon groups, such as heteroatoms, within the organic group.

[0093] R a10 Substituents other than hydrocarbon groups among the organic groups are not particularly limited as long as the effects of the present invention are not impaired. Specific examples of such substituents include halogen atoms, hydroxyl groups, mercapto groups, sulfide groups, cyano groups, isocyano groups, cyanato groups, isocyanato groups, thiocyanato groups, isothiocyanato groups, silyl groups, silanol groups, alkoxy groups, alkoxycarbonyl groups, carbamoyl groups, thiocarbamoyl groups, nitro groups, nitroso groups, carboxyl groups, carboxylate groups, acyl groups, acyloxy groups, sulfino groups, sulfo groups, sulfonato groups, phosphino groups, phosphinyl groups, phosphono groups, phosphonato groups, hydroxyimino groups, alkyl ether groups, alkyl thioether groups, aryl ether groups, aryl thioether groups, N-monosubstituted amino groups, and N,N-disubstituted amino groups. The hydrogen atoms included in the above substituents may be substituted by hydrocarbon groups. Additionally, the hydrocarbon groups included in the above substituents may be of the straight-chain type, branched-chain type, and cyclic type.

[0094] R a10 As for the group, an alkyl group, an aryl group, an aralkyl group, or a complex ring group is preferred. These groups may be substituted with a halogen atom, a hydroxyl group, an alkyl group, or a complex ring group. In addition, if these groups include an alkylene portion, the alkylene portion may be interrupted by an ether bond, a thioether bond, or an ester bond.

[0095] When the alkyl group is a straight-chain alkyl group or a branched-chain alkyl group, the number of carbon atoms is preferably 1 or more and 20 or less, more preferably 1 or more and 15 or less, and particularly preferably 1 or more and 10 or less. Examples of preferred alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n-decyl group, isodecyl group, etc.

[0096] When the alkyl group is an alicyclic group or a group containing an alicyclic group, preferred alicyclic groups included in the alkyl group may include monocyclic alicyclic groups such as cyclopentyl groups and cyclohexyl groups, or polycyclic alicyclic groups such as adamantyl groups, norbornyl groups, isobornyl groups, tricyclononyl groups, tricyclodecyl groups, and tetracyclododecyl groups.

[0097] Preferable examples other than comonomers include (meth)acrylamides, unsaturated carboxylic acids, allyl compounds, vinyl ethers, vinyl esters, styrenes, etc. These comonomers may be used alone or in combination of two or more types.

[0098] (Meth)acrylamides include (meth)acrylamide; N-alkyl (meth)acrylamides such as N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, Nn-propyl (meth)acrylamide, N-isopropyl (meth)acrylamide, and Nn-butyl (meth)acrylamide; N-aryl (meth)acrylamides such as N-phenyl (meth)acrylamide, N-α-naphthyl (meth)acrylamide, and N-β-naphthyl (meth)acrylamide; N,N-dialkyl (meth)acrylamides such as N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N,N-di-n-propyl (meth)acrylamide, and N,N-di-n-butyl (meth)acrylamide; Examples include N,N-diaryl(meth)acrylamides such as N,N-diphenyl(meth)acrylamide; N-methyl-N-phenyl(meth)acrylamide; and other N,N-disubstituted (meth)acrylamides such as N-hydroxyethyl-N-methyl(meth)acrylamide.

[0099] Examples of unsaturated carboxylic acids include monocarboxylic acids such as crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; and anhydrides of these dicarboxylic acids.

[0100] Examples of allyl compounds include allyl esters such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, and allyl lactate; allyl oxyethanol; etc.

[0101] Examples of vinyl ethers include alkyl vinyl ethers such as hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, etc.; vinyl aryl ethers such as vinylphenyl ether, vinyltolyl ether, vinylchlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, vinyl anthranil ether, etc.

[0102] Examples of vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl phenyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenyl butyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthosate, etc.

[0103] Styrenes include styrene; alkylstyrenes such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, etc.; alkoxystyrenes such as methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, etc.; chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc., halostyrenes such as chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc.

[0104] When copolymerizing a monomer having a primary amino group and a comonomer, the ratio of the monomer having a primary amino group to the comonomer is not particularly limited. For example, the ratio of the two, on a molar basis, as monomer having a primary amino group : comonomer, is preferably 5 to 50 : 50 to 95, more preferably 10 to 40 : 60 to 90, and even more preferably 15 to 30 : 70 to 85.

[0105] Compounds represented by formula (a2) include the following formula (a2-1):

[0106] [Chemical Formula 6]

[0107]

[0108] (In Equation (a2-1), R a01 , R a02 , R a2 , R a3 , R a4 and R a6 is R in equation (a2) a01 , R a02 , R a2 , R a3 , R a4 and R a6 It is identical to.)

[0109] Examples of compounds represented by can be found.

[0110] The compound represented by formula (a2) can be obtained, for example, by a Diels-Alder reaction between the compound represented by the following formula and a conjugated diene compound corresponding to the structure of the compound represented by formula (a2).

[0111] The conditions for this Diels-Alder reaction can be appropriately set according to the type of raw material used, and the reaction may also be carried out in an organic solvent.

[0112] [Chemical Formula 7]

[0113]

[0114] Organic solvents used in the Diels-Alder reaction include, for example, esters such as ethyl acetate, butyl acetate, and cellosolve acetate; ketones such as acetone, methyl ethyl ketone, isobutyl ketone, and methyl isobutyl ketone; esters such as ethyl acetate, butyl acetate, and diethyl malonicate; amides such as N-methylpyrrolidone and N,N-dimethylformamide; ethers such as diethyl ether, ethylcyclopentyl ether, tetrahydrofuran, and dioxane; aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as hexane, heptane, octane, and decahydronaphthalene; halogenated hydrocarbons such as methylene chloride and ethylene chloride; and dimethyl sulfoxide and dimethyl sulfoamide. For organic solvents, one type of solvent may be used, or two or more types may be used in any combination.

[0115] The reaction temperature is, for example, in the range of -10 ℃ to 200 ℃, preferably in the range of 0 ℃ to 150 ℃, and more preferably in the range of 5 ℃ to 120 ℃.

[0116] As for the reaction time, for example, it is 5 minutes or more and 12 hours or less, 10 minutes or more and 10 hours or less, and 30 minutes or more and 8 hours or less.

[0117] The condensation in the first process is typically carried out using a condensation agent. Examples of dehydration condensation agents include carbodiimide compounds such as carbonyldiimidazole or N,N'-diisopropylcarbodiimide.

[0118] The addition of this condensation agent may be carried out in the reaction vessel in which the aforementioned Diels-Alder reaction was performed, or the product from the Diels-Alder reaction may be isolated separately and then dissolved again in an organic solvent or the like to be added.

[0119] The organic solvent used in this condensation process may be the same organic solvent used in the Diels-Alder reaction.

[0120] The reaction temperature is, for example, in the range of -10 ℃ to 200 ℃, preferably in the range of 0 ℃ to 150 ℃, and more preferably in the range of 5 ℃ to 120 ℃.

[0121] As for the reaction time, for example, it is 5 minutes or more and 12 hours or less, 10 minutes or more and 10 hours or less, and 30 minutes or more and 8 hours or less.

[0122] The compound having the group represented by the above formula (a3) ​​obtained by carrying out the first process may be isolated after carrying out the first process.

[0123] When the compound having the group represented by the above formula (a3) ​​is a resin, this isolation is carried out by, for example, solidifying the reaction solution after the condensation in the first process by pouring it into a solvent, and then filtering and collecting the result.

[0124] In the second process, the compound having the group represented by formula (a3) ​​produced in the first process is heated to convert the group represented by formula (a3) ​​into the group represented by formula (a1) (reverse Diels-Alder reaction). Thus, a maleimide modified compound (A) having the group represented by formula (a1) is obtained.

[0125] The group represented by the above formula (a1) can be introduced into all or part of the amino groups derived from the monomer having a primary amino group, which is the raw material compound, depending on the amount of the compound represented by the formula (a2).

[0126] The reverse Diels-Alder reaction in the second process is carried out, for example, in an organic solvent. As the organic solvent, the same organic solvent used in the aforementioned Diels-Alder reaction may be used. Since the reaction is carried out by heating, the boiling point of the organic solvent is preferably 60°C or higher, more preferably 80°C or higher, and even more preferably 100°C or higher. There is no particular upper limit for the boiling point, but for example, it is 350°C or lower.

[0127] Regarding the heating of the second process, the reaction temperature is, for example, in the range of 60°C to 280°C, preferably in the range of 80°C to 250°C, and more preferably in the range of 100°C to 225°C.

[0128] The reaction time is, for example, 5 minutes or more and 12 hours or less, preferably 10 minutes or more and 10 hours or less, and more preferably 30 minutes or more and 8 hours or less.

[0129] The compound having the group represented by the above formula (a1) obtained by carrying out the second process may be isolated after carrying out the second process.

[0130] When the compound having the group represented by the above formula (a1) is a resin, this isolation is carried out by, for example, solidifying the reaction solution after the condensation in the second process by pouring it into a non-solvent (e.g., an alcohol-based solvent) and collecting it by filtering.

[0131] As an example of a method for preparing a maleimide modified compound (A), a reaction scheme is shown below in which a copolymer of aminostyrene, a monomer having a primary amino group, and styrene, a comonomer, is used as a raw material compound having a primary amino group. In the reaction scheme below, the second step is shown as an example of refluxing in toluene. Also, in the reaction scheme below, m and n are each the number of repetitions of the constituent unit.

[0132] [Chemical Formula 8]

[0133]

[0134] According to the method for manufacturing such a maleimide modified compound (A), side reactions other than maleimidation are suppressed. In particular, when manufacturing a maleimide modified resin (A1), the above method suppresses side reactions, and as a result, a maleimide modified resin (A1) having a group represented by formula (a1) can be obtained in a solid state. Therefore, for example, a maleimide modified resin (A1) having a group represented by formula (a1) can be incorporated into the above curable composition as a solid resin. For example, a polymer of a monomer having an unsaturated double bond containing a group represented by formula (a1) at the end of the side chain could not conventionally be obtained as a solid resin because there was a problem with gelation. Specifically, for example, in a method of ring-closing by reacting maleic anhydride with a styrene resin having an amino group, gelation occurred and a solid resin could not be obtained. This can be attributed to the fact that side reactions other than the desired maleimidation are likely to occur. However, according to the above manufacturing method, a polymer of a monomer having an unsaturated double bond containing a group represented by formula (a1) is obtained as a solid resin.

[0135] In addition, in the specification of the present application, the substituted or unsubstituted cyclic imide group represented by formula (a1) is also referred to as a “maleimide group” for convenience.

[0136] According to the above manufacturing method, instead of polymerizing a monomer into which a maleimide group has been introduced, a pre-polymerized polymer is used as a raw material compound, and a group represented by formula (a1) is introduced by reacting the primary amino group of the polymer, so the polymerization is not limited to time-consuming cationic polymerization. Therefore, the above manufacturing method is a simple method.

[0137] After generating a group represented by formula (a3) ​​by condensing a primary amino group with a dicarboxylic acid anhydride represented by formula (a2), the group represented by formula (a3) ​​is converted into a group represented by formula (a1) by heating, so the group represented by formula (a1) can be reliably introduced without causing problems due to a ring-closing reaction.

[0138] <Maleimide-modified polyphenylene ether resin (A1-1)>

[0139] For the above, regarding the maleimide modified compound (A), the description has mainly focused on the maleimide modified resin (A1), but a maleimide modified polyphenylene ether resin (A1-1) having a group represented by formula (a1) is also preferred as the maleimide modified resin (A1). The maleimide modified polyphenylene ether resin (A1-1) is preferably a resin in which the molecular chain ends of an unmodified polyphenylene ether resin are modified by terminal groups comprising the group represented by formula (a1). The structure of the terminal group comprising the group represented by formula (a1) is not particularly limited to the extent that it does not impede the purpose of the present invention.

[0140] The phenylene group included in the main chain of the maleimide-modified polyphenylene ether resin (A1-1) may have 1 to 4 substituents.

[0141] If the maleimide-modified polyphenylene ether resin (A1-1) has a terminal group comprising a group represented by formula (a1), the terminal group is of the following formula (Ai):

[0142] *-Y 2 -Y 1 -** ··· (Ai)

[0143] It is preferable to interpose a linker represented by to bond to the main chain of the maleimide-modified polyphenylene ether resin (A1-1).

[0144] The bonding hand on the ** side of the linker is bonded to an oxygen atom originating from a hydroxyl group at the end of the molecular chain of the unmodified polyphenylene ether resin that gives the maleimide-modified polyphenylene ether resin (A1-1). On the other hand, the bonding hand on the * side of the linker is bonded to the end group.

[0145] Among equations (Ai), Y 1 It is a single bond, or a carbonyl group. Y 2 is a 2-valent organic group. Y 1 In the case of this single bond, Y 1 The single bond as is, Y 2 It bonds to a carbon atom that takes an sp3 hybrid orbital among the organic groups of the divalent group.

[0146] In equation (Ai), Y 1 In the case of this carbonyl group, Y 2 Ga, -Y 4 -Y 3 It is desirable that it be represented as -. Y 3 It is a single bond, -O-, or -NH-. Y 4 is a 2-valent organic group. Y 3 This Y 1 It combines with the carbonyl group as.

[0147] In short, Y in equation (Ai) 1 In the case of this carbonyl group, the linker represented by formula (Ai) is preferably a group represented by the following formulas (Ai-1) to (Ai-3).

[0148] *-Y 4 -CO-** ··· (Ai-1)

[0149] *-Y 4 -O-CO-** ··· (Ai-2)

[0150] *-Y 4 -NH-CO-** ··· (Ai-3)

[0151] Y 4 The organic group of 2 as is Y 3The organic group is not particularly limited as long as it can connect to the terminal group represented by formula (a1). The structure of the organic group may be a straight chain, a branched chain, a ring, or a combination of these structures. Heteroatoms other than carbon and hydrogen atoms that the organic group may include nitrogen atoms, sulfur atoms, oxygen atoms, halogen atoms, phosphorus atoms, silicon atoms, and boron atoms. The organic group may have one or more unsaturated bonds.

[0152] Y 4 Hydrocarbon groups are preferred in that the compound used for terminal modification in maleimide-modified polyphenylene ether resin (A1-1) is easy to obtain or manufacture, and the desired terminal modification is easy.

[0153] The number of carbon atoms in the hydrocarbon group is preferably 1 or more and 10 or less, more preferably 1 or more and 8 or less, and even more preferably 1 or more and 6 or less.

[0154] The hydrocarbon group can be an aliphatic hydrocarbon or an aromatic hydrocarbon. As for the hydrocarbon group, an aromatic hydrocarbon is preferred because it is flexible compared to rigid aromatic hydrocarbons.

[0155] Y 4 Preferred hydrocarbon groups include methylene group, ethane-1,2-diyl group, ethane-1,1-diyl group, propane-1,3-diyl group, propane-1,2-diyl group, propane-1,1-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, cyclohexane-1,4-diyl group, cyclohexane-1,3-diyl group, cyclohexane-1,2-diyl group, p-phenylene group, m-phenylene group, o-phenylene group, naphthalene-1,4-diyl group, naphthalene-2,6-diyl group, and Naphthalene-2,7-diyl group can be cited.

[0156] Among these, ethane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, cyclohexane-1,4-diyl group, and cyclohexane-1,3-diyl group are preferred.

[0157] In equation (Ai), Y 1 In the case of this single bond, Y 1 The single bond as is, Y 2 It bonds to a carbon atom taking an sp3 hybrid orbital among the divalent organic groups as. The carbon atom taking an sp3 hybrid orbital is typically, Y 2 It is a carbon atom that constitutes the entire structure or partial structure of an aliphatic hydrocarbon group in an organic group.

[0158] In equation (Ai), Y 1 In the case of this single bond, Y 2 The divalent organic group as is not particularly limited, provided it is a group having at least one carbon atom taking an sp3 hybrid orbital and capable of connecting an oxygen atom derived from a hydroxyl group at the end of the molecular chain of the unmodified polyphenylene ether resin conferring the terminal maleimide-modified polyphenylene ether resin (A1-1) and a terminal group represented by formula (a1). Y 1 In the case where this is a single bond, Y 2 The divalent organic group as may include one or more heteroatoms, such as nitrogen atoms, sulfur atoms, oxygen atoms, halogen atoms, phosphorus atoms, silicon atoms, and boron atoms, in addition to carbon atoms and hydrogen atoms.

[0159] Y 1 In the case of this single bond, Y 2 The number of carbon atoms of the 2-valent organic group is preferably 1 or more and 10 or less, more preferably 1 or more and 8 or less, and even more preferably 1 or more and 6 or less.

[0160] Y 1 In the case of this single bond, Y 2The 2-valent organic group as is preferably an aliphatic hydrocarbon group in which one or more methylene groups may be substituted with a carbonyl group (-CO-), an ether bond (-O-), or an imino group (-NH-).

[0161] Y 1 In the case of this single bond, Y 2 Preferred aliphatic hydrocarbon groups include methylene, ethane-1,2-diyl, ethane-1,1-diyl, propane-1,3-diyl, propane-1,2-diyl, propane-1,1-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, cyclohexane-1,4-diyl, cyclohexane-1,3-diyl, and cyclohexane-1,2-diyl. In addition, it is also preferable that one or two methylene groups of these hydrocarbon groups be substituted with a carbonyl group (-CO-), an ether bond (-O-), or an imino group (-NH-).

[0162] Among these, ethane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, cyclohexane-1,4-diyl group, and cyclohexane-1,3-diyl group are preferred.

[0163] The method of modifying an unmodified polyphenylene ether resin by introducing a terminal group represented by formula (a1) to the end of the molecular chain is not particularly limited.

[0164] To carry out such modification, an unmodified polyphenylene ether resin having phenolic hydroxyl terminals is preferably used.

[0165] The unmodified polyphenylene ether resin may be a resin having at least one phenolic hydroxyl group terminal. The unmodified polyphenylene ether resin preferably has two or more phenolic hydroxyl group terminals, more preferably has two or three phenolic hydroxyl group terminals, and even more preferably has two phenolic hydroxyl group terminals.

[0166] In addition, when the unmodified polyphenylene ether resin has a phenolic hydroxyl group at the end, the unmodified polyphenylene ether resin may additionally have a phenolic hydroxyl group on the phenylene group included in the main chain.

[0167] Polyphenylene ether resin can typically be produced by oxidatively polymerizing a phenol compound, such as 2,6-dimethylphenol, in the presence of a catalyst containing a metal, such as copper. Although the method for producing unmodified polyphenylene ether resin is not particularly limited, it is preferable to produce unmodified polyphenylene ether resin according to known methods or the typical method described above.

[0168] The phenylene group included in the main chain of the maleimide-modified polyphenylene ether resin (A1-1) may have one or more and four or fewer substituents. For this reason, the phenylene group included in the main chain of the unmodified polyphenylene ether resin may also have one or more and four or fewer substituents.

[0169] Examples of substituents include alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl groups; aromatic hydrocarbon groups having 1 to 4 carbon atoms, such as phenyl, o-tolyl, m-tolyl, and p-tolyl groups; alkoxy groups having 1 to 4 carbon atoms, such as methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, and tert-butyloxy; phenolic hydroxyl groups; and halogen atoms, such as fluorine, chlorine, bromine, and iodine atoms, are preferred.

[0170] Among these substituents, methyl groups, phenyl groups, chlorine atoms, and bromine atoms are preferred, and methyl groups, phenyl groups, and chlorine atoms are more preferred.

[0171] Examples of unmodified polyphenylene ether resins include homopolymers of phenols or copolymers of two or more phenols.

[0172] The unmodified polyphenylene ether resin may be a polymer obtained by polymerizing only monovalent phenol, or a polymer obtained by copolymerizing monovalent phenol with polyvalent phenols such as divalent phenol or trivalent phenol.

[0173] A polymer of 1 phenol alone has an aryl group derived from raw material phenol that does not have a hydroxyl group at one end, and a hydroxyaryl group derived from raw material phenol at the other end.

[0174] In copolymers of monovalent phenol and polyvalent phenol, molecular chains of polyphenylene ether grow from two or more phenolic hydroxyl groups of the polyvalent phenol. For this reason, when monovalent phenol is copolymerized with divalent phenol, a polyphenylene ether resin having hydroxyaryl groups at both ends is obtained. When monovalent phenol is copolymerized with trivalent or higher phenol, a polyphenylene ether resin having branched chains corresponding to the hydration of the polyvalent phenol and hydroxyaryl groups at the ends of each branched chain is obtained.

[0175] Specific examples of homopolymers of phenols include poly(2,6-dimethyl-1,4-phenylene ether), poly(2-methyl-6-phenyl-1,4-phenylene ether), and poly(2,6-dichloro-1,4-phenylene ether).

[0176] As mentioned above, the copolymer of two or more phenols may be a copolymer of two or more monovalent phenols, or a copolymer of one or more monovalent phenols and one or more divalent phenols.

[0177] Specific examples of copolymers of two or more monovalent phenols include copolymers of 2,6-dimethylphenol and 2,3,6-trimethylphenol, copolymers of 2,6-dimethylphenol and 2,6-dichlorophenol, and copolymers of 2,6-dimethylphenol and 2-methyl-6-phenylphenol.

[0178] Examples of copolymers of one or more monovalent phenols and one or more divalent phenols include a copolymer of 3,3',5,5'-tetramethylbisphenol A polymerized with 2,6-dimethylphenol, a copolymer of 3,3',5,5'-tetramethylbisphenol A polymerized with 2-methyl-6-phenylphenol, or a copolymer of 3,3',5,5'-tetramethylbisphenol A polymerized with 2,6-dichlorophenol.

[0179] As for the unmodified polyphenylene ether resin, a copolymer of 3,3',5,5'-tetramethylbisphenol A, which is a copolymer of monovalent phenol and divalent phenol, a copolymer of 2,6-dimethylphenol polymerized with 3,3',5,5'-tetramethylbisphenol A, a copolymer of 2-methyl-6-phenylphenol polymerized with 3,3',5,5'-tetramethylbisphenol A, and a copolymer of 2,6-dichlorophenol polymerized with 3,3',5,5'-tetramethylbisphenol A are preferred, and a copolymer of 3,3',5,5'-tetramethylbisphenol A polymerized with 2,6-dimethylphenol is more preferred.

[0180] The method of modifying an unmodified polyphenylene ether resin to introduce a terminal group represented by formula (a1) at the end is not particularly limited.

[0181] For example, Y in equation (Ai) 1 This is a carbonyl group, and the linker represented by formula (Ai) is the following formula (Ai-1):

[0182] *-Y 4 -CO-** ··· (Ai-1)

[0183] In the case of a cause represented by , MIG-Y 4 By condensing the phenolic hydroxyl groups of the unmodified polyphenylene ether resin with a carboxylic acid represented by -CO-OH using a condensing agent such as carbonyldiimidazole or a carbodiimide-based compound such as N,N'-diisopropylcarbodiimide, the terminal phenolic hydroxyl groups of the unmodified polyphenylene ether resin are converted to -O-CO-Y 4It can be converted into a group represented by -MIG. Also, MIG is a terminal group represented by equation (a1).

[0184] Also, MIG-Y 4 By reacting a carboxylic acid halide represented as -CO-Hal with the phenolic hydroxyl groups of an unmodified polyphenylene ether resin, the terminal phenolic hydroxyl groups of the unmodified polyphenylene ether resin are modified to -O-CO-Y 4 It can be converted into a group represented by -MIG. Also, Hal is a halogen atom, such as a chlorine atom or a bromine atom.

[0185] Y in equation (Ai) 1 This is a carbonyl group, and the linker represented by formula (Ai) is the following formula (Ai-2):

[0186] *-Y 4 -O-CO-** ··· (Ai-2)

[0187] In the case of the group represented by , the phenolic hydroxyl groups of the unmodified polyphenylene ether resin and the excess amount of MIG-Y with respect to the phenolic hydroxyl groups 4 By reacting an alcohol represented by -OH with a compound that forms carbonate bonds, such as phosgene or triphosgene, the terminal phenolic hydroxyl groups of the unmodified polyphenylene ether resin are -O-CO-OY 4 It can be converted into a unit represented by -MIG.

[0188] Y in equation (Ai) 1 This is a carbonyl group, and the linker represented by formula (Ai) is the following formula (Ai-3):

[0189] *-Y 4 -NH-CO-** ··· (Ai-3)

[0190] In the case of a group represented as such, the phenolic hydroxyl groups possessed by the unmodified polyphenylene ether resin, MIG-Y 4By reacting with an isocyanate represented by -NCO, the terminal phenolic hydroxyl groups of the unmodified polyphenylene ether resin are modified to -O-CO-NH-Y 4 It can be converted into a unit represented by -MIG.

[0191] Y in equation (Ai) 1 In the case of this single bond, the phenolic hydroxyl groups of the unmodified polyphenylene ether resin and MIG-Y 2 By etherifying a halide represented by -Hal by a method such as the so-called Williamson ether synthesis, the terminal phenolic hydroxyl groups of the unmodified polyphenylene ether resin are -OY 2 It can be converted into a unit represented by -MIG.

[0192] Although representative methods for modifying phenolic hydroxyl groups have been described above, methods for modifying phenolic hydroxyl groups are not limited to these methods. As methods for modifying phenolic hydroxyl groups, various known methods may be employed depending on the structure of the linker that binds to the terminal group represented by formula (a1).

[0193] In the above modification method, an organic solvent according to the reaction employed may be appropriately used as needed. Regarding the reaction temperature or reaction time, known preferred conditions for the reaction employed may also be appropriately adopted.

[0194] When preparing a maleimide-modified polyphenylene ether resin (A1-1) using an unmodified polyphenylene ether resin, a group including a terminal group represented by formula (a1) may be introduced to some of the phenolic hydroxyl groups of the unmodified polyphenylene ether resin, or a group including a terminal group represented by formula (a1) may be introduced to all of the phenolic hydroxyl groups.

[0195] The molecular weight of the maleimide-modified polyphenylene ether resin (A1-1) is not subject to any particular limitation as long as it does not impede the effects of the present invention. The mass average molecular weight (Mw) is preferably 2,000 or more, more preferably 2,500 or more, and even more preferably 3,000 or more. The molecular weight of the maleimide-modified polyphenylene ether resin (A1-1) is preferably 100,000 or less as the mass average molecular weight (Mw), more preferably 80,000 or less, even more preferably 50,000 or less, and even more preferably 10,000 or less.

[0196] Although a maleimide modified resin (A1) having a group represented by formula (a1) has been described above, a maleimide modified monomer (A2) having a group represented by formula (a1), which is a maleimide modified compound (A) other than the maleimide modified resin (A1), may be an example of a bismaleimide compound in which two amino groups of an aromatic diamine or an aliphatic diamine are substituted with a group represented by formula (a1).

[0197] Specific examples of aromatic diamines include p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 1,4-bis-(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, Examples include bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, and 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane.

[0198] Specific examples of aliphatic diamines include pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, 2,3,3-trimethylpentane-1,5-diamine, etc.

[0199] Commercially available and readily available maleimide modified monomers (A2) include 2,2-bis[4-(4-maleimidephenoxy)phenyl]propane and the following compounds (all manufactured by Tokyo Kasei Kogyo Co., Ltd.), as well as BMI-689, BMI-1400, BMI-1500, BMI-1700, BMI-2700, and BMI-3000 (all manufactured by Designer Molecules Co., Ltd.).

[0200] [Chemical Formula 9]

[0201]

[0202] In this way, a maleimide modified compound (A) having a terminal group represented by formula (a1) at the end of the molecular chain can be polymerized by exposure to light or heating because the terminal group represented by formula (a1) is a radical polymerizable group. As a result of polymerization, the maleimide modified compound (A) provides an insulating film with a low dielectric constant, a low dielectric loss tangent, and excellent heat resistance. For example, the dielectric constant of the formed insulating film can be less than 3.00. Also, the dielectric loss tangent of the formed insulating film can be less than 0.01. Also, the glass transition temperature (Tg) of the formed insulating film can be 150°C or higher.

[0203] A curable composition containing a maleimide modified compound (A) has excellent film-forming properties in a coating method. For this reason, when a film is formed by a coating method using this curable composition, there is no occurrence of cracks or crystals, no tack (stickiness), and good compatibility of the components. Therefore, an insulating film can be formed by a coating method, which is an easy method.

[0204] The maleimide modified compound (A) has excellent solvent solubility. Therefore, a curable composition containing the maleimide modified compound (A) can be applied to a developing process using the solvent as a negative type composition.

[0205] In particular, the maleimide modified compound (A) may be soluble in an alkaline aqueous solution, depending on its structure. For example, the maleimide modified compound (A) may have an alkali-soluble group such as a carboxyl group or a phenolic hydroxyl group. A curable composition containing such an alkali-soluble maleimide modified compound (A) can be applied to an alkali development process as a negative type composition.

[0206] A curable film of a desired pattern shape can be formed by applying position-selective exposure and the development process to a coating film made of a curable composition comprising a maleimide modified compound (A).

[0207] The content of the maleimide modified compound (A) in the curable composition is not particularly limited. The content of the maleimide modified compound (A) is preferably 5 mass% or more and 100 mass% or less with respect to the total solid content of the curable composition.

[0208] When the curable composition comprises a maleimide modified compound (A), a maleimide modified resin (A1), and a maleimide modified monomer (A2), the ratio W1:W2 of the mass W1 of the maleimide modified resin (A1) and the mass W2 of the maleimide modified monomer (A2) is preferably 10:90 to 90:10, and more preferably 20:80 to 80:20. The ratio W1:W2 may be 30:70 to 70:30, or 40:60 to 60:40.

[0209] [Radical polymerizable compound (B)]

[0210] The curable composition may additionally include a radical polymerizable compound (B). Of course, the curable composition may not include a radical polymerizable compound (B).

[0211] Radical polymerizable compound (B) is a radical polymerizable compound other than maleimide modified compound (A).

[0212] The radical polymerizable compound (B) may be a compound having unsaturated double bonds, such as styrene, styrene polymer, acrylonitrile, (meth)acrylic acid, (meth)acrylic acid ester, etc.

[0213] As the above radical polymerizable compound, various radical polymerizable compounds that have conventionally been incorporated into radical polymerizable compositions may be used without special limitations. Specific examples of radical polymerizable compounds other than maleimide compounds include the following compounds.

[0214] Monofunctional radical polymerizable compounds include (meth)acrylamide, methylol(meth)acrylamide, methoxymethyl(meth)acrylamide, ethoxymethyl(meth)acrylamide, propoxymethyl(meth)acrylamide, butoxymethoxymethyl(meth)acrylamide, N-methylol(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamide-2-methylpropanesulfonic acid, tert-butylacrylamidesulfonic acid, methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, cyclohexyl(meth)acrylate, Examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-(meth)acryloyloxy-2-hydroxypropyl phthalate, glycerin mono(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylamino(meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, and half (meth)acrylates of phthalic acid derivatives. These monofunctional compounds may be used alone or in combination of two or more.

[0215] Polyfunctional radical polymerizable compounds include 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, ethoxylated hexanediol di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, 2-hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate, dipentaerythritol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and dipropylene glycol di(meth)acrylate. Tripropylene glycol di(meth)acrylate, ethoxylated neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, poly(ethylene-propylene) glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, propoxylated ethoxylated bisphenol A di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanedyl glycol di(meth)acrylate, Trimethylolpropane tri(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 2,2-bis(4-(meth)acryloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxypolyethoxyphenyl)propane, 2-hydroxy-3-(meth)acryloyloxypropyl(meth)acrylate,Ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalate diglycidyl ester di(meth)acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly(meth)acrylate, urethane (meth)acrylate (i.e., tolylene diisocyanate), reaction products of trimethylhexamethylene diisocyanate and hexamethylene diisocyanate, etc. with 2-hydroxyethyl (meth)acrylate, methylenebis(meth)acrylamide, (meth)acrylamide methylene ether, condensate of polyhydric alcohol and N-methylol (meth)acrylamide, triacrylformal, 2,4,6-trioxohexahydro-1,3,5-triazine-1,3,5-trisethanol triacrylate, and Examples include 2,4,6-trioxohexahydro-1,3,5-triazine-1,3,5-trisethanol diacrylate. These polyfunctional compounds may be used individually or in combination of two or more.

[0216] The content of the radical polymerizable compound (B) in the curable composition is not particularly limited, but it is preferable to have a content of 10 mass% or more and 70 mass% or less with respect to the total amount of the maleimide modified compound (A) and the radical polymerizable compound (B).

[0217] [Radical generator (C)]

[0218] The curable composition comprises a radical generator (C). The radical generator (C) may be a photoradical generator (C1) or a thermal radical generator (C2), and may use a combination of a photoradical generator (C1) and a thermal radical generator (C2).

[0219] Examples of photoradical generators (C1) include alkylphenone-based generators such as Omnirad 651, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127, Omnirad 907, Omnirad 369, Omnirad 369E, and Omnirad 379EG (all manufactured by IGM Resins BV), acylphosphine oxide-based generators such as Omnirad TPO H and Omnirad 819 (all manufactured by IGM Resins BV), and oxime ester-based photopolymers such as Irgacure OXE01 and Irgacure OXE02 (all manufactured by BASF).

[0220] Specific examples of photoradical generators (C1) include 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis(4-dimethylaminophenyl)ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyloxime) (Irgacure OXE01), ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyloxime) (Irgacure OXE02), 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Omnirad TPO H), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (Omnirad 819), 4-benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, 4-methylaminobenzoate, 4-ethyldimethylaminobenzoate, 4-dimethylaminobenzoate, 4-butyldimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-Dimethylamino-2-isoamylbenzoic acid, Benzyl-β-methoxyethylacetal, Benzyldimethylketal, 1-Phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, O-methyl benzoylbenzoate, 2,4-Diethylthioxanthone, 2-Chlorothioxanthone, 2,4-Dimethylthioxanthone, 1-Chloro-4-Propoxythioxanthone, Thioxanthene, 2-Chlorothioxanthene, 2,4-Diethylthioxanthene, 2-Methylthioxanthene, 2-Isopropylthioxanthene, 2-Ethylanthraquinone, Octamethylanthraquinone, 1,2-Benzanthraquinone, 2,3-Diphenylanthraquinone, Azobisisobutyronitrile, Benzoyl peroxide, Cumene hydroperoxide, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-(O-chlorophenyl)-4,5-di(m-methoxyphenyl)-imidazolyl dimer, benzophenone, 2-chlorobenzophenone, p,p'-Bisdimethylaminobenzophenone, 4,4'-Bisdiethylaminobenzophenone, 4,4'-Dichlorobenzophenone, 3,3-Dimethyl-4-Methoxybenzophenone, Benzyl, Benzoin, Benzoin methyl ether, Benzoin ethyl ether, Benzoin isopropyl ether, Benzoin-n-butyl ether, Benzoin isobutyl ether, Benzoin butyl ether, Acetophenone, 2,2-Diethoxyacetophenone, p-Dimethylacetophenone, p-Dimethylaminopropiophenone, Dichloroacetophenone, Trichloroacetophenone, p-tert-Butylacetophenone, p-Dimethylaminoacetophenone, p-tert-Butyltrichloroacetophenone, p-tert-Butyldichloroacetophenone, α,α-Dichloro-4-Phenoxyacetophenone, Thioxanthone, 2-Methylthioxanthone, 2-Isopropylthioxanthone, Dibenzosuberone, Pentyl-4-Dimethylaminobenzoate, 9-Phenylacridine, 1,7-Bis-(9-Acridinyl)Heptane, 1,5-Bis-(9-Acridinyl)Pentane, 1,3-Bis-(9-Acridinyl)Propane, p-Methoxytryazine, 2,4,6-Tris(Trichloromethyl)-s-Triazine, 2-Methyl-4,6-Bis(Trichloromethyl)-s-Triazine, 2-[2-(5-Methylfuran-2-yl)ethenyl]-4,6-Bis(Trichloromethyl)-s-Triazine, 2-[2-(furan-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-methylphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyl-s-triazine, Examples include 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl-s-triazine, and 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl-s-triazine. These photoradical generators includeIt can be used alone or in combination of two or more types. Among these, using an oxime-based generator is particularly desirable in terms of sensitivity.

[0221] As thermal radical generators (C2), ketone peroxides (methyl ethyl ketone peroxide and cyclohexanone peroxide, etc.), peroxyketals (2,2-bis(tert-butylperoxy)butane and 1,1-bis(tert-butylperoxy)cyclohexane, etc.), hydroperoxides (tert-butyl hydroperoxide and cumene hydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide (perbutyl (registered trademark) D (manufactured by Nichiyu Co., Ltd.), and di-tert-hexyl peroxide (perhexyl (registered trademark) D (manufactured by Nichiyu Co., Ltd.)), diacyl peroxides (isobutyryl peroxide, lauroyl peroxide and benzoyl peroxide, etc.), peroxydicarbonates (diisopropyl peroxydicarbonate, etc.), peroxyesters (tert-butyl peroxyisobutyrate and Organic peroxides such as 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, etc., or 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), 2,2'-azobis(2-methylpropionamidine)dihydrochloride, 2,2'-azobis[2-methyl-N-(2-propenyl)propionamidine]dihydrochloride, 2,2'-azobis(2-methylpropionamide), 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2'-azobis(2-methylpropane), Examples of azo compounds include 2,2'-azobis(2,4,4-trimethylpentane) and dimethyl 2,2'-azobis(2-methylpropionate), etc.

[0222] The content of the radical generator (C) in the curable composition is not particularly limited, but with respect to 100 parts by mass of the total mass of the maleimide modified compound (A) and the radical polymerizable compound (B), it is preferably 0.1 parts by mass or more and 10 parts by mass or less, more preferably 0.5 parts by mass or more and 10 parts by mass or less, and even more preferably 2 parts by mass or more and 10 parts by mass or less.

[0223] <Thiol Compound (D)>

[0224] The curable composition comprises a thiol compound (D) together with a maleimide modified compound (A). By doing so, the curable composition imparts a cured product with excellent elongation and tensile strength.

[0225] The number of mercapto groups in the thiol compound (D) is not particularly limited. The number of mercapto groups in the thiol compound (D) is preferably 2 or more, more preferably 2 to 10, and even more preferably 2 to 6, in order to make it easier to obtain a cured product with excellent elongation and tensile strength.

[0226] Specific examples of compounds having two or more mercapto groups include 1,2-benzenedithiol, 1,3-benzenedithiol, 1,4-benzenedithiol, 1,2-bis(mercaptomethyl)benzene, 1,3-bis(mercaptomethyl)benzene, 1,4-bis(mercaptomethyl)benzene, 1,2-bis(mercaptoethyl)benzene, 1,3-bis(mercaptoethyl)benzene, 1,4-bis(mercaptoethyl)benzene, 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris(mercaptomethyl)benzene, 1,2,4-tris(mercaptomethyl)benzene, and 1,3,5-tris(mercaptomethyl)benzene. 1,2,3-Tris(mercaptoethyl)benzene, 1,2,4-Tris(mercaptoethyl)benzene, 1,3,5-Tris(mercaptoethyl)benzene, 2,5-Toluenedithiol, 3,4-Toluenedithiol, 1,3-Di(p-methoxyphenyl)propane-2,2-dithiol, 1,3-Diphenylpropane-2,2-dithiol, Phenylmethane-1,1-dithiol, 2,4-Di(p-mercaptophenyl)pentane, 1,2-Bis(mercaptoethylthio)benzene, 1,3-Bis(mercaptoethylthio)benzene, 1,4-Bis(mercaptoethylthio)benzene, 1,2,3-Tris(mercaptomethylthio)benzene, 1,2,4-Tris(mercaptomethylthio)benzene, Examples include 1,3,5-tris(mercaptomethylthio)benzene, 1,2,3-tris(mercaptoethylthio)benzene, 1,2,4-tris(mercaptoethylthio)benzene, and 1,3,5-tris(mercaptoethylthio)benzene.

[0227] As for the thiol compound (D) having two or more mercapto groups, a mercaptoalkanoate of a polyol having two or more hydroxyl groups is preferred due to the ease of obtaining or synthesizing it and the stability of dissolution in a curable composition.

[0228] The mercaptoalkanoate of a polyol having two or more hydroxyl groups may have hydroxyl groups, but it is preferable that it does not have hydroxyl groups.

[0229] The number of carbon atoms of the mercaptoalkanoic acid imparting the mercaptoalkanoate is not particularly limited, but is preferably 2 or more and 6 or less, and preferably 3 or 4. Specific examples of the mercaptoalkanoic acid imparting the mercaptoalkanoate include thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 2-mercaptobutoic acid, 3-mercaptobutoic acid, 4-mercaptobutoic acid, 2-mercaptopentanoic acid, 3-mercaptopentanoic acid, 4-mercaptopentanoic acid, 5-mercaptopentanoic acid, 2-mercaptohexanoic acid, 3-mercaptohexanoic acid, 4-mercaptohexanoic acid, and 5-mercaptohexanoic acid.

[0230] Among these, 2-mercaptopropionic acid and 3-mercaptobutanoic acid are preferred.

[0231] Polyols that impart mercaptoalkanoates may include aromatic groups.

[0232] Polyols that do not contain aromatic groups include ethylene glycol, 1,3-propanediol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, 1,4-cyclohexanediol, 1,3-cyclohexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, glycerin, diglycerin, triglycerin, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol, mannitol, sorbitan, sucrose, Examples include glucose, mannose, methylglucoside, and tris(2-hydroxyethyl)isocyanuric acid.

[0233] Aromatic polyols include benzenediols such as hydroquinone, resorcinol, and catechol; benzenediols such as phloroglucinol, pyrogallol, and 1,2,4-benzenetriol; naphthalenediols such as 1,2-naphthalenediol, 1,3-naphthalenediol, 1,4-naphthalenediol, 1,5-naphthalenediol, 1,6-naphthalenediol, 1,7-naphthalenediol, 1,5-naphthalenediol, 2,3-naphthalenediol, 2,6-naphthalenediol, and 2,7-naphthalenediol; Examples include naphthalenttriols such as 1,4,5-naphthalenttriol, 1,2,4-naphthalenttriol, 1,3,8-naphthalenttriol, and 1,2,7-naphthalenttriol; bisphenols such as bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol S, and bisphenol Z; tetrahydroxybiphenyls such as 3,3',4,4'-tetrahydroxybiphenyl and 3,3',5,5'-tetrahydroxybiphenyl; calixarenes; and novolak resins such as phenol novolak, cresol novolak, and naphthol novolak.

[0234] Among the above polyols, ethylene glycol, 1,3-propanediol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, glycerin, diglycerin, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, and tris(2-hydroxyethyl)isocyanuric acid are preferred, and 1,4-butanediol, trimethylolethane, trimethylolpropane, pentaerythritol, and tris(2-hydroxyethyl)isocyanuric acid are more preferred.

[0235] Preferably among the mercaptoalkanoates of the polyols described above are 1,4-butanediol di(2-mercaptopropionate), 1,4-butanediol di(3-mercaptobutanoate), trimethylol ethane tri(2-mercaptopropionate), trimethylol ethane tri(3-mercaptobutanoate), trimethylolpropane tri(2-mercaptopropionate), trimethylolpropane tri(3-mercaptobutanoate), pentaerythritol tetra(2-mercaptopropionate), pentaerythritol tetra(3-mercaptobutanoate), tris(2-hydroxyethyl)isocyanuric acid tri(2-mercaptopropionate), and tris(2-hydroxyethyl)isocyanuric acid tri(3-mercaptobutanoate). 1,4-butanediol di(3-mercaptobutanoate), trimethylolethane tri(3-mercaptobutanoate), trimethylolpropane tri(3-mercaptobutanoate), pentaerythritol tetra(3-mercaptobutanoate), and tris(2-hydroxyethyl)isocyanuric acid tri(3-mercaptobutanoate) are more preferred.

[0236] The amount of thiol compound (D) used is not particularly limited as long as it does not impede the purpose of the present invention. The amount of thiol compound (D) used is preferably 0.1 parts by mass or more and 20 parts by mass or less, more preferably 0.5 parts by mass or more and 15 parts by mass or less, and even more preferably 1 part by mass or more and 12 parts by mass or less, based on 100 parts by mass of the total mass of the maleimide modified compound (A) and the radical polymerizable compound (B).

[0237] <Protonic acid (E)>

[0238] It is preferable that the curable composition includes a proton acid (E). When the curable composition includes a thiol compound (D) together with a maleimide modified compound (A), the curable composition may be prone to changes in viscosity over time. However, when the curable composition includes a proton acid (E) together with a thiol compound (D), the stability of the curable composition over time can be increased. Here, proton acid refers to proton H ＋ It refers to a compound capable of releasing.

[0239] In addition, if the maleimide modified compound (A) has an acidic group that acts as a proton acid, such as a carboxyl group or a phenolic hydroxyl group, the curable composition containing said maleimide modified compound (A) is said to contain a proton acid (E).

[0240] As for the proton acid, it may be an organic acid or an inorganic acid, but an organic acid is preferred.

[0241] Specific examples of organic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, isovaleric acid, acrylic acid, methacrylic acid, oxalic acid, phthalic acid, benzoic acid, salicylic acid, 4-hydroxybenzoic acid, lactic acid, citric acid, tartaric acid, malonic acid, malic acid, succinic acid, glycolic acid, glutamic acid, aspartic acid, maleic acid, caproic acid, caprylic acid, myristic acid, stearic acid, palmitic acid, pyruvate, ascorbic acid, adipic acid, phenol, 1-naphthol, 2-naphtholmethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, methylphosphonic acid, ethylphosphonic acid, and phenylphosphonic acid.

[0242] Specific examples of inorganic acids include hydrochloric acid, hydrobromide, sulfuric acid, nitric acid, and phosphoric acid.

[0243] The amount of proton acid (E) used is not particularly limited as long as it does not impede the purpose of the present invention. The amount of proton acid (E) used is preferably 0.1 parts by mass or more and 5 parts by mass or less, more preferably 0.2 parts by mass or more and 3 parts by mass or less, with respect to 100 parts by mass of the total mass of the maleimide modified compound (A) and the radical polymerizable compound (B), and even more preferably 0.5 parts by mass or more and 1.5 parts by mass or less.

[0244] <Organic Solvent (S)>

[0245] The curable composition typically includes an organic solvent (S). The type of organic solvent (S) is not particularly limited to a range that does not impede the purpose of the present invention, and can be appropriately selected from organic solvents conventionally used in curable compositions.

[0246] Specific examples of organic solvents (S) include ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; polyhydric alcohols such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, and monophenyl ether of ethylene glycol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether acetate, dipropylene glycol, and dipropylene glycol monoacetate, and their derivatives; cyclic ethers such as dioxane; Examples include esters such as ethyl formate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl pyruvate, ethyl ethoxyacetate, methyl methoxypropionate, ethyl ethoxypropionate, 2-methyl hydroxypropionate, 2-ethyl hydroxypropionate, 2-hydroxy-2-methylpropionate, 2-hydroxy-3-methylbutanoic acid, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate; aromatic hydrocarbons such as toluene and xylene; etc. These may be used individually or in combination of two or more types.

[0247] The content of the organic solvent (S) is not particularly limited as long as it does not impede the purpose of the present invention. It is preferable to use the organic solvent (S) in a range where the solid content concentration of the curable composition is 30 mass% or more and 70 mass% or less.

[0248] [Other Additives]

[0249] The curable composition may additionally contain a maleimide curing agent to improve curability, and may additionally contain a surfactant to improve applicability, anti-foaming properties, leveling properties, etc.

[0250] Examples of maleimide curing agents include diamines, allyl compounds such as low-polarity polyfunctional allylphenol resins (e.g., FATC-809, FATC-AE (both manufactured by Gun-Ai Chemical Industry Co., Ltd.)) or allyl ethers, 1-propenyl compounds having a 1-propenyl group such as propenified biphenylene resins (e.g., BPN (manufactured by Gun-Ai Chemical Industry Co., Ltd.)), and benzoxazine compounds.

[0251] As surfactants, for example, fluorine-based surfactants or silicone-based surfactants are preferably used.

[0252] Specific examples of fluorine-based surfactants include commercially available fluorine-based surfactants such as BM-1000, BM-1100 (both manufactured by BM Chem), MegaPac F142D, MegaPac F172, MegaPac F173, MegaPac F183 (all manufactured by Dainippon Ink Chemical Co., Ltd.), Florad FC-135, Florad FC-170C, Florad FC-430, Florad FC-431 (all manufactured by Sumitomo 3M), Surfron S-112, Surfron S-113, Surfron S-131, Surfron S-141, Surfron S-145 (all manufactured by Asahi Glass Co.), SH-28PA, SH-190, SH-193, SZ-6032, and SF-8428 (all manufactured by Toray Silicon Co., Ltd.), but are not limited to these.

[0253] As silicone-based surfactants, unmodified silicone-based surfactants, polyether-modified silicone-based surfactants, polyester-modified silicone-based surfactants, alkyl-modified silicone-based surfactants, aralkyl-modified silicone-based surfactants, and reactive silicone-based surfactants may be preferably used.

[0254] Commercially available silicone surfactants may be used as silicone surfactants. Specific examples of commercially available silicone surfactants include Paintard M (manufactured by Toray Dow Corning), Topeka K1000, Topeka K2000, Topeka K5000 (all manufactured by Takachiho Sangyo Co.), XL-121 (polyether-modified silicone surfactant, manufactured by Clariant), and BYK-310 (polyester-modified silicone surfactant, manufactured by BYK Chem).

[0255] The curable composition may contain an antioxidant. The antioxidant is not particularly limited and conventionally known antioxidants may be used. Examples include hindered phenol-based antioxidants (e.g., Irganox 1010 (manufactured by BASF)), hindered amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, etc.

[0256] The curable composition may contain a polymerization inhibitor to appropriately prevent polymerization during the reaction. The polymerization inhibitor is not particularly limited and may use conventionally known polymerization inhibitors, such as methoquinone, hydroquinone, methylhydroquinone, p-methoxyphenol, pyrogallol, tert-butylcatechol, phenothiazine, etc.

[0257] When forming an insulating film using a curable composition, the curable composition may contain an adhesion enhancer to improve adhesion between a metal wiring or a substrate for an electrical or electronic device having metal wiring and the insulating film formed using the curable composition. The adhesion enhancer is not particularly limited and may use conventionally known adhesion enhancers, such as benzotriazole.

[0258] [Method for preparing a curable composition]

[0259] The curable composition is prepared by mixing and stirring each of the above components in a conventional manner. Devices that can be used when mixing and stirring each of the above components include a dissolver, a homogenizer, a three-roll mill, etc. After uniformly mixing each of the above components, the resulting mixture may be further filtered using a mesh, a membrane filter, etc.

[0260] In addition, it is also preferable to make the curable composition a multi-agent mixed type curable composition comprising two or more agents, including a first agent containing a maleimide modified compound (A) and a second agent containing a thiol compound (D). When the maleimide modified compound (A) and the thiol compound (D) coexist in the curable composition, the curable composition may be prone to change over time. However, if the above multi-agent mixed type curable composition is used, such a problem of change over time does not occur.

[0261] The above multi-agent mixed curable composition may be, for example, a multi-agent mixed composition of three or more agents including a third agent additionally including a radical generator (C). However, for ease of mixing during use, the multi-agent mixed curable composition is preferably a two-agent mixed curable composition comprising a first agent including a maleimide modified compound (A) and a second agent including a thiol compound (D).

[0262] For such a two-part mixed curable composition, each of the first part comprising a maleimide modified compound (A) and the second part comprising a thiol compound (D) may optionally include one or more components other than the maleimide modified compound (A) and the thiol compound (D). Additionally, in the two-part mixed curable composition, either the first part or the second part comprises a radical generator (C).

[0263] ≪Method for Forming an Insulating Film≫

[0264] An insulating film is formed using the above-mentioned curable composition.

[0265] The method for forming an insulating film is,

[0266] A coating process for forming a coating film by applying a curable composition to an insulating film formation site, and

[0267] It includes a curing process for curing the coating film.

[0268] Preferably, by using a curable composition, an insulating film that insulates metal wiring in an electrical or electronic device having metal wiring can be formed.

[0269] In a method for forming an insulating film, for example, a curable composition is applied at least at an insulating film formation point on a substrate for an electrical or electronic device having metal wiring, and a coating film is formed.

[0270] Methods such as spin coating, slit coating, roll coating, screen printing, inkjet, and applicator methods may be employed as the application method for the curable composition. When applying printing methods such as screen printing or inkjet, it is possible to apply the curable composition only to the points where the insulating film is to be formed.

[0271] The thickness of the coating film is not particularly limited, but is preferably 0.5 μm or more, more preferably 0.5 μm or more and 300 μm or less, particularly preferably 1 μm or more and 150 μm or less, and most preferably 3 μm or more and 50 μm or less.

[0272] Next, if necessary, drying or pre-baking is performed on the coating film. The pre-baking conditions vary depending on the type of each component in the curable composition, the mixing ratio, the thickness of the coating film, etc., but are typically at 70°C or higher and 200°C or lower, preferably at 80°C or higher and 150°C or lower, for 2 minutes or more and 120 minutes or less.

[0273] When the curable composition includes a photoradical generator (C1), the coating film is irradiated (exposed) with active light or radiation, for example, ultraviolet or visible light with a wavelength of 300 nm or more and 500 nm or less. The entire surface of the coating film may be exposed, or the exposure (pattern exposure) may be performed selectively by a method such as exposing the active light or radiation through a mask of a predetermined pattern.

[0274] By exposure to light, a polymerization component, a maleimide modified compound (A) or a radical polymerizable compound (B), polymerizes to form an insulating film. Thus, an insulating film is formed on a substrate for an electrical or electronic device having metal wiring, for example.

[0275] As a radiation source, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, argon gas lasers, etc., may be used. In addition, radiation includes microwaves, infrared rays, visible light, ultraviolet rays, X-rays, gamma rays, electron beams, proton beams, neutron beams, ion beams, etc. The radiation dose varies depending on the composition of the curable composition or the thickness of the coating film, but for example, in the case of using an ultra-high-pressure mercury lamp, it is 100 mJ / cm² or more and 10,000 mJ / cm² or less. In addition, the radiation may include light that activates a radical generator (C) to generate radicals.

[0276] In the case of position-selective exposure, the exposed coating film is developed according to a conventionally known method, and an insulating film of a predetermined shape is formed by dissolving and removing unnecessary parts. At this time, the above-mentioned organic solvent (S) or an alkaline aqueous solution may be used as the developer. For example, if the above-mentioned maleimide modified compound (A) has an alkali-soluble group such as a carboxyl group or a phenolic hydroxyl group, development with an alkaline aqueous solution is possible.

[0277] As an alkaline aqueous solution used as a developer, for example, an aqueous solution of alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide (tetramethylammonium hydroxide), tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo[5,4,0]-7-undecene, and 1,5-diazabicyclo[4,3,0]-5-nonane may be used. In addition, an aqueous solution in which an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant is added to the above-mentioned aqueous solution of alkalis may be used as a developer.

[0278] The development time varies depending on the composition of the curable composition or the thickness of the coating film, but is typically between 1 minute and 30 minutes. The development method may be any of the liquid mounting method, dipping method, paddle method, spray development method, etc.

[0279] After development, for example, rinse with water for 30 seconds or more and 90 seconds or less, and dry using an air gun or oven, etc.

[0280] In this way, for example, an insulating film patterned in a desired shape is formed on a substrate for an electrical or electronic device having metal wiring.

[0281] In addition, the above describes an example in which an insulating film is formed by polymerizing a polymerization component, a maleimide modified compound (A) or a radical polymerizable compound (B), by exposure to light. When the curable composition includes a thermal radical generator (C2), an insulating film may be formed by polymerizing the polymerization component, a maleimide modified compound (A) or a radical polymerizable compound (B), by heating.

[0282] Since the formed insulating film has a low dielectric constant and a low dielectric loss tangent, it is suitable as an insulating film for electrical and electronic devices having metal wiring for high-frequency applications. For example, it can be used as an insulating film for electrical and electronic devices having metal wiring for frequencies in the 5G communication band candidate range of 3 GHz to 30 GHz or millimeter wave band range of 30 GHz to 300 GHz. In addition, since the formed insulating film has excellent heat resistance, it is suitable for applications where components such as wiring are further formed by heating after the insulating film is formed.

[0283] Examples

[0284] The present invention will be explained in more detail below by way of examples, but the present invention is not limited to these examples.

[0285] [Preparation Example 1]

[0286] As an unmodified polyphenylene ether resin, a polyphenylene ether resin having phenolic hydroxyl terminals of the following structure (SA90, manufactured by SABIC Innovative Plastics) was used.

[0287] [Chemical Formula 10]

[0288]

[0289] 166 parts by mass of unmodified polyphenylene ether resin and 47.2 parts by mass of a carboxylic acid having a maleimide group of the following structure were added to 1184 parts by mass of dichloroethane.

[0290] [Chemical Formula 11]

[0291]

[0292] 40.9 parts by mass of diisopropylcarbodiimide and 0.25 parts by mass of dimethylaminopyridine were added to the reaction mixture, and a reaction to modify terminal phenolic hydroxyl groups was carried out at 5°C for 8 hours. After the reaction, the reaction mixture was filtered and reprecipitated with acetonitrile to obtain 145 parts by mass of maleimide-modified polyphenylene ether resin A1, in which the phenolic hydroxyl groups at both ends of the unmodified polyphenylene ether resin were modified into groups of the following formula. The mass average molecular weight (Mw) of the maleimide-modified polyphenylene ether resin A1, measured by gel permeation chromatography (GPC), was 7000 in polystyrene equivalent.

[0293] [Chemical Formula 12]

[0294]

[0295] [Preparation Example 2]

[0296] As resin A2, a maleimide-modified resin was prepared in which the amino group in the copolymer of styrene and 4-aminostyrene was modified.

[0297] 72.8 parts by mass of a copolymer having a copolymerization ratio of styrene and 4-aminostyrene of 80 / 20 (mol) as styrene / 4-aminostyrene (mol), and 41 parts by mass of oxonorbornene anhydride represented by the following formula were dissolved in 300 parts by mass of tetrahydrofuran and stirred for 4 hours under a nitrogen atmosphere.

[0298] [Chemical Formula 13]

[0299]

[0300] Next, 61 parts by mass of carbonyldiimidazole were added to the reaction solution, and the reaction solution was stirred for 6 hours. Afterward, the reaction solution was added dropwise to 1,500 parts by mass of heptane to recover the precipitated polymer having the following structure. In the following structural formula, the number at the bottom right of the parentheses in each constituent unit indicates the content (mol%) of the constituent unit in each resin.

[0301] [Chemical Formula 14]

[0302]

[0303] The obtained polymer of the above structure was mixed with a 20 mass% toluene solution and stirred for 4 hours while refluxing. Afterwards, by reprecipitating with heptane, 17.8 mass parts of a solid resin A2 of the following structure were obtained.

[0304] 13 The maleimide structure was confirmed from the carbonyl peak and the double bond peak in 1C NMR. In addition, 13 The solvent for the 1C NMR measurement was acetone-d6.

[0305] In addition, the mass average molecular weight (Mw) of the obtained resin A2 was determined by polystyrene conversion using gel permeation chromatography (GPC). The mass average molecular weight (Mw) of resin A2 was 15,000.

[0306] [Chemical Formula 15]

[0307]

[0308] <Preparation of Curable Composition>

[0309] [Examples 1 to 14, and Comparative Examples 1 to 4]

[0310] In Examples 1 to 14, the resins A1, A2 and the following A3 were used as maleimide modified compounds (A).

[0311] Also, A3 is BMI-689 (manufactured by Designer Molecules).

[0312] [Chemical Formula 16]

[0313]

[0314] In Examples 1 to 14 and Comparative Examples 1 to 4, the following C1 and C2 were used as radical generators (C).

[0315] C1 : Irgacure OXE02 (Manufactured by BASF)

[0316] C2: Perhexyl D (manufactured by Nichiyu Co.)

[0317] In Examples 1 to 14, the following D1 and D2 were used as thiol compounds (D).

[0318] D1 : Pentaerythritol tetra(3-mercaptobutanoate)

[0319] D2 : Tris(2-hydroxyethyl)isocyanuric acid tri(3-mercaptobutanoate)

[0320] In Examples 1 to 8 and Examples 11 to 14, the following E1 to E3 were used as protic acid (E).

[0321] E1: Phenylphosphonic acid

[0322] E2: Salicylic acid

[0323] E3: Malonic acid

[0324] In Examples 1 to 14 and Comparative Examples 1 to 4, the following F1 to F3 were used as additives.

[0325] F1: Irganox 1010 (Manufactured by BASF)

[0326] F2 : FATC-809 (Maleimide curing agent, low-polarity polyfunctional allylphenol resin (manufactured by Gun-Ei Chemical Industry Co., Ltd.))

[0327] F3 : FATC-AE (Maleimide curing agent, low-polarity polyfunctional allylphenol resin (manufactured by Gun-Ai Chemical Industry Co., Ltd.))

[0328] Curable compositions of each example and comparative example were obtained by dissolving maleimide modified compound (A), radical generator (C), thiol compound (D), proton acid (E), additive, and 0.05 mass parts of surfactant (BYK310, manufactured by BYK Chem) of the types and amounts listed in Tables 1 to 2, respectively, in propylene glycol monomethyl ether acetate (PGMEA) so that the solid content concentration was 40 mass%.

[0329] <Evaluation>

[0330] Using the obtained curable composition, film formation properties, photolithography characteristics, dielectric constant, dielectric loss tangent, and heat resistance were evaluated according to the following methods. The results of these evaluations are listed in Tables 1 and 2.

[0331] [Metastatic and Photolithographic Characteristics]

[0332] The curable compositions of the examples and comparative examples were applied onto a Si substrate with a diameter of 200 mm to form a coating film. Subsequently, the coating film was pre-baked (PAB) at 80°C for 200 seconds. In addition, the film thickness of the coating film after pre-baking was 11 μm. After pre-baking, a pattern was exposed using ghi lines at an exposure amount of 100 mJ / cm² or more and 4400 mJ / cm² or less, using a hole pattern mask capable of forming a circular opening with a diameter of 30 μm and an exposure device Prisma GHI5452 (manufactured by Ultratec). In addition, the focus was set to 0 μm (coating film surface).

[0333] Next, the substrate was placed on a hot plate and heated (PEB) after exposure at 90°C for 1.5 minutes. After that, the exposed coating film was immersed in propylene glycol monomethyl ether acetate (PGMEA) at 60°C for 60 seconds. Then, nitrogen blowing was performed, and the film was heated at 180°C for 1 hour under a nitrogen atmosphere to obtain a pattern (insulating film).

[0334] The surface of the coating film prior to pre-baking was observed using a scanning electron microscope to evaluate film formation properties. Specifically, ○ was used when no cracks and / or crystals were observed on the pattern surface, there was no tack (stickiness) on the pattern, and the contained components were in use and transparent. Additionally, a was used when cracks were observed on the pattern surface, b was used when crystals were observed on the pattern surface, c was used when there was tack (stickiness) on the pattern surface, and d was used when the contained components were not in use and the surface was opaque, and × was used when at least one of a to d was present.

[0335] In addition, the surface and cross-section of the obtained pattern (insulating film) were observed using a scanning electron microscope to evaluate the photolithography characteristics. Specifically, within the exposure amount range described above, if a condition existed where an aperture of 30 μm in diameter was formed, it was evaluated as ○, and if a condition did not exist where an aperture of 30 μm in diameter was formed, it was evaluated as ×.

[0336] [Permittivity and Dielectric Loss Tangent]

[0337] The curable compositions of the examples and comparative examples were applied onto a Si substrate with a diameter of 200 mm to form a coating film. Subsequently, the coating film was pre-baked (PAB) at 80 °C for 200 seconds. Furthermore, the film thickness of the coating film after pre-baking was 11 μm. After pre-baking, the entire surface was exposed to ghi lines using an exposure device Prisma GHI5452 (manufactured by Ultratec) at an exposure amount of 4400 mJ / cm². Additionally, the focus was set to 0 μm (coating film surface). Afterward, the surface of the coating film was nitrogen-blowed and heated at 180 °C for 1 hour under a nitrogen atmosphere to obtain a sample.

[0338] The permittivity (ε) and dielectric loss tangent (tanδ) of the obtained sample were measured using the method described in "Review of Millimeter Wave Complex Permittivity Evaluation by Cylindrical Cavity Resonance Technique of Photosensitive Insulating Films" (Kohei Takahagi (University of Utsunomiya), Kazuaki Ebisawa (Tokyo Ohka Industrial Co., Ltd.), Yoshinori Kogami (University of Utsunomiya), Takashi Shimizu (University of Utsunomiya)) in the New Journal of Electronics, Information and Communications Technology, Vol. 118, No. 506, MW2018-158, pp. 13-18, March 2019. Using a network analyzer HP8510C (manufactured by Keysight), measurements were taken using the cavity resonance technique under conditions of room temperature 25°C, humidity 50%, frequency 36 GHz, and sample thickness 10 μm.

[0339] The permittivity was evaluated by marking ○ when the permittivity value was less than 3.00 and × when it was 3.00 or greater.

[0340] The genetic loss tangent was evaluated by marking ○ when the value was less than 0.01 and × when it was 0.01 or greater.

[0341] [Heat resistance]

[0342] For samples obtained by the same method as in [Permittivity and Dielectric Loss Tangent], the peak top temperature (°C) of tanδ measured using a dynamic viscoelasticity measuring device Rheogel-E4000 (manufactured by UBM Co., Ltd.) was set as the glass transition point (Tg) (DMA method). The measurement conditions were as follows: measurement mode: tensile mode, frequency: 10 Hz, heating rate: 5°C / min, measurement temperature range: 40 to 300°C, sample shape: length 50 mm, width 5 mm, thickness 10 μm.

[0343] Heat resistance was evaluated by marking ○ when Tg was 150 ℃ or higher and × when Tg was less than 150 ℃.

[0344] [Elongation and Tensile Strength]

[0345] A short, book-shaped test specimen with a width of 1 cm and a length of 5 cm was cut from a film obtained by peeling the film from a Si substrate. Tensile tests were performed on the obtained test specimen using an EZ-test (manufactured by Shimadzu Corporation) at a length of 2 cm and a tensile speed of 1 mm / min to measure elongation and tensile strength. The length of the length at the fracture point was determined as the elongation.

[0346] Regarding height, ○ was used when the height measured by the above method was 8% or more, and × was used when it was less than 8%.

[0347] Regarding tensile strength, ○ was used when the tensile strength measured by the above method was 90 MPa or higher, and × was used when it was less than 90 MPa.

[0348] [Storage Stability]

[0349] The curable composition of each example was stored at room temperature for one week, and ○ was used to indicate that it did not gel, and × was used to indicate that it gelled.

[0350]

[0351]

[0352]

[0353]

[0354] According to Examples 1 to 14, it can be seen that if a curable composition comprising a maleimide modified compound (A), a radical generator (C), and a thiol compound (D) is used, a curable film with excellent dielectric properties, heat resistance, elongation, and tensile strength can be formed, which has excellent film-forming properties and photolithography characteristics and can be preferably used as an insulating film.

[0355] Meanwhile, according to Comparative Examples 1 to 4, it can be seen that even if the curable composition contains a maleimide modified compound (A), it is difficult to achieve both excellent elongation and excellent tensile strength for the cured film when it does not contain a thiol compound (D).

[0356] In addition, from a comparison with Examples 9 and 10 and other examples, it can be seen that when the curable composition contains a thiol compound (D) together with a maleimide modified compound (A), gelation over time is likely to occur, but by adding protic acid (E) to the curable composition, gelation over time is suppressed.

Claims

Claim 1 Comprising a maleimide modified compound (A), a radical generator (C), a thiol compound (D), and a proton acid (E), wherein the maleimide modified compound (A) is of the following formula (a1): The group represented by has one or more groups, and the group represented by formula (a1) is bonded to a carbon atom in an aliphatic hydrocarbon group or an aromatic group in the maleimide modified compound (A), and in formula (a1), R a01 and R a02 Each is independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and the thiol compound (D) is an ester of a polyol having 2 or more hydroxyl groups and a mercaptoalkano acid, provided that the ester does not have hydroxyl groups, and the proton acid (E) is formic acid, acetic acid, propionic acid, butyric acid, valeric acid, isovaleric acid, oxalic acid, phthalic acid, benzoic acid, salicylic acid, 4-hydroxybenzoic acid, lactic acid, citric acid, tartaric acid, malonic acid, malic acid, succinic acid, glycolic acid, glutamic acid, aspartic acid, maleic acid, caproic acid, caprylic acid, myristic acid, stearic acid, palmitic acid, pyruvate, ascorbic acid, adipic acid, phenol, A curable composition comprising 1-naphthol, 2-naphtholmethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, methylphosphonic acid, ethylphosphonic acid, or phenylphosphonic acid, wherein the amount of the radical generator (C) used is 0.1 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the maleimide modified compound (A), the amount of the thiol compound (D) used is 0.1 parts by mass or more and 20 parts by mass or less per 100 parts by mass of the maleimide modified compound (A), and the amount of the proton acid (E) used is 0.1 parts by mass or more and 5 parts by mass or less per 100 parts by mass of the maleimide modified compound (A). Claim 2 A curable composition according to claim 1, wherein the radical generator (C) comprises a photoradical generator (C1), and the curable composition can be cured by exposure to light. Claim 3 A curable composition according to claim 1 or 2, wherein the maleimide modified compound (A) is a maleimide modified polyphenylene ether resin (A1-1). Claim 4 A curable composition according to claim 1 or 2, wherein the thiol compound (D) is 3-mercaptobutanoate of the polyol. Claim 5 A curable composition of the multi-agent mixed type, comprising two or more agents, wherein the first agent comprising the maleimide modified compound (A) and the second agent comprising the thiol compound (D). Claim 6 A curable composition used for forming an insulating film according to claim 1 or 2. Claim 7 A cured product of the curable composition described in claim 1 or 2. Claim 8 A method for forming an insulating film, comprising: a coating process of forming a coating film by applying a curable composition described in claim 1 or 2 to an insulating film formation site, and a curing process of curing the coating film. Claim 9 A method for forming an insulating film according to claim 8, wherein the curable composition comprises a photoradical generator (C1) as the radical generator (C), and the coating film is cured by exposure to light. Claim 10 A method for forming an insulating film according to claim 9, further comprising a developing process in which the exposure to the coating film is performed selectively by position, and the exposed coating film is developed by a developer. Claim 11 delete Claim 12 delete Claim 13 delete

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