Curable composition for forming an insulating film, method for forming an insulating film, and terminal maleimide modified polyphenylene ether resin

Abstract

The invention provides a curable composition that can be preferably applied to the formation of an insulating film, capable of forming a cured product with low dielectric constant and dielectric loss tangent and excellent heat resistance, and also having excellent film-forming properties, a method for forming an insulating film using said curable composition, and a terminal maleimide modified polyphenylene ether resin preferably used as a component of the said curable composition. A terminal maleimide modified polyphenylene ether resin (A) having a radical polymerizable group having a specific structure including a maleimide backbone at the end of the molecular chain, and a radical generator (C) are combined in the curable composition.

Description

Technology Field

[0001] The present invention relates to a curable composition used to form an insulating film, a method for forming an insulating film, and a terminal maleimide modified polyphenylene ether resin. 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. In such a situation, 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 additional components, such as wiring, to be formed by heating after an insulating film is formed using a composition. For this reason, heat resistance is also required for the insulating film.

[0009] When forming an insulating film with a composition, the insulating film can be easily formed using 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] The present invention has been made in consideration of the above problem and aims to provide a curable composition that can be preferably applied to the formation of an insulating film, a curable composition capable of forming a cured product with low dielectric constant and dielectric loss tangent and excellent heat resistance and excellent film-forming properties, a method for forming an insulating film using said curable composition, and a terminal maleimide modified polyphenylene ether resin preferably used as a component of the said curable composition. means of solving the problem

[0011] The inventors have discovered that a curable composition comprising a terminal maleimide modified polyphenylene ether resin (A) having a radical polymerizable group of a specific structure including a maleimide backbone at the end of the molecular chain provides an insulating film with low dielectric constant and dielectric loss tangent and excellent heat resistance, and also has excellent film-forming properties, thereby completing the present invention.

[0012] A first aspect of the present invention is a curable composition comprising a terminal maleimide modified polyphenylene ether resin (A) and a radical generator (C), wherein

[0013] Terminal maleimide modified polyphenylene ether resin (A) a, the following formula (a1):

[0014] [Chemical Formula 1]

[0015]

[0016] Having terminal groups represented by at the ends of the molecular chain,

[0017] 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, and

[0018] The phenylene group included in the main chain of the terminal maleimide-modified polyphenylene ether resin (A) may have 1 to 4 substituents, and

[0019] The terminal unit, the following formula (a2):

[0020] *-Y 2 -Y 1 -** … (a2)

[0021] By interposing a linker represented by, it is bonded to the main chain of a terminal maleimide-modified polyphenylene ether resin (A), and

[0022] A 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 an unmodified polyphenylene ether resin (A') that gives the terminal maleimide-modified polyphenylene ether resin (A), and

[0023] The coupling hand on the * side of the connector is coupled to the end device, and

[0024] In equation (a2), Y 1 It is a single bond, or a carbonyl group, and Y 2 is an organic group of 2, and Y 1 In the case of this single bond, Y 1 The single bond as is, Y 2 Bonded to a carbon atom taking an sp3 hybrid orbital among the 2-valent organic groups as, and

[0025] It is a curable composition used for forming an insulating film.

[0026] A second aspect of the present invention is a curable composition comprising a terminal maleimide modified polyphenylene ether resin (A) and a radical generator (C), wherein

[0027] Terminal maleimide modified polyphenylene ether resin (A) a, the following formula (a1):

[0028] [Chemical Formula 2]

[0029]

[0030] Having terminal groups represented by at the ends of the molecular chain,

[0031] 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, and

[0032] The phenylene group included in the main chain of the terminal maleimide-modified polyphenylene ether resin (A) may have 1 to 4 substituents, and

[0033] The radical generator (C) is a curable composition in which the photoradical generator (C1) is a photoradical generator.

[0034] A third aspect of the present invention is the following formula (a1):

[0035] [Chemical Formula 3]

[0036]

[0037] Having terminal groups represented by at the ends of the molecular chain,

[0038] 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, and

[0039] The phenylene group included in the main chain of the terminal maleimide-modified polyphenylene ether resin (A) may have 1 to 4 substituents, and

[0040] The terminal unit, the following formula (a2):

[0041] *-Y 2 -Y 1 -** … (a2)

[0042] By interposing a linker represented by, it is bonded to the main chain of a terminal maleimide-modified polyphenylene ether resin (A), and

[0043] A 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 an unmodified polyphenylene ether resin (A') that gives the terminal maleimide-modified polyphenylene ether resin (A), and

[0044] The coupling hand on the * side of the connector is coupled to the end device, and

[0045] In equation (a2), Y 1 It is a single bond, or a carbonyl group, and Y 2 is an organic group of 2, and Y 1 In the case of this single bond, Y 1 The single bond as is, Y 2 It is a terminal maleimide modified polyphenylene ether resin that is bonded to a carbon atom taking an sp3 hybrid orbital among the 2 valent organic groups. Effects of the invention

[0046] According to the present invention, a curable composition that can be preferably applied to the formation of an insulating film, which can form a cured product having low dielectric constant and dielectric loss tangent and excellent heat resistance and also has excellent film-forming properties, a method for forming an insulating film using said curable composition, and a terminal maleimide modified polyphenylene ether resin preferably used as a component of the said curable composition can be provided. Brief explanation of the drawing

[0047] FIG. 1 shows the terminal maleimide modified polyphenylene ether resin P1 obtained in Preparation Example 1 and the unmodified polyphenylene ether resin (SA90). 1 This is a diagram showing the H NMR measurement results. Specific details for implementing the invention

[0048] Curable composition

[0049] The curable composition comprises a terminal maleimide modified polyphenylene ether resin (A) and a radical generator (C), and

[0050] Terminal maleimide modified polyphenylene ether resin (A) a, the following formula (a1):

[0051] [Chemical Formula 4]

[0052]

[0053] Having a terminal group represented by at the end of the molecular chain, and

[0054] In equation (a1), R a01 and R a02 a, each 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

[0055] Examples include a first curable composition and a second curable composition, wherein the phenylene group included in the main chain of the terminal maleimide modified polyphenylene ether resin (A) may have 1 to 4 substituents as a common feature.

[0056] Hereinafter, the first curable composition and the second curable composition will be described.

[0057] <First Curable Composition>

[0058] The first curable composition is a curable composition comprising a terminal maleimide modified polyphenylene ether resin (A) and a radical generator (C).

[0059] As described above, the terminal maleimide modified polyphenylene ether resin (A) is of the following formula (a1):

[0060] [Chemical Formula 5]

[0061]

[0062] It has a terminal group represented by at the end of the molecular chain.

[0063] In equation (a1), R a01 and R a02 Each is independently 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.

[0064] The phenylene group included in the main chain of the terminal maleimide modified polyphenylene ether resin (A) may have 1 to 4 substituents.

[0065] In the terminal maleimide modified polyphenylene ether resin used in the first curable composition, the terminal group is of the following formula (a2):

[0066] *-Y 2 -Y 1 -** … (a2)

[0067] By interposing a linker represented by, it is bonded to the main chain of the terminal maleimide modified polyphenylene ether resin (A).

[0068] 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 an unmodified polyphenylene ether resin (A') that gives the end maleimide-modified polyphenylene ether resin (A). Meanwhile, the bonding hand on the * side of the linker is bonded to the end group.

[0069] In equation (a2), 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.

[0070] The first curable composition is used to form an insulating film. Typically, the first curable composition is used to form an insulating film that insulates metal wiring in an electrical or electronic device having metal wiring.

[0071] 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.

[0072] 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 having various layers or components formed on a silicon substrate.

[0073] This metal wiring and other metal wiring or conductive members are insulated by an insulating film formed by the first curable composition.

[0074] By using a first 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, the first 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.

[0075] In addition, since it can form an insulating film with excellent heat resistance, the first curable composition can be used, for example, to form an insulating film in an electrical or electronic device in which another member is formed by heating after forming an insulating film with the curable composition.

[0076] In addition, the first 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 the components, so an insulating film can be formed by the coating method, which is an easy method.

[0077] The first curable composition will be described in detail below.

[0078] [Terminal maleimide modified polyphenylene ether resin (A)]

[0079] The first curable composition contains a terminal maleimide modified polyphenylene ether resin (A) having a terminal group represented by the following formula (a1) at the end of the molecular chain.

[0080] In addition, in the specification of the present application, the substituted or unsubstituted cyclic imide group represented by formula (a1) is also referred to for convenience as a “maleimide group.”

[0081] [Chemical Formula 6]

[0082]

[0083] (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.

[0084] 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.

[0085] R in equation (a1) a01 and Ra02 Specific examples of cycloalkyl groups having 3 to 8 carbon atoms include cyclopropyl groups, cyclobutyl groups, cyclopentyl groups, and cyclohexyl groups.

[0086] 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.

[0087] 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 terminal maleimide-modified polyphenylene ether resin (A) has excellent polymerization properties. For this reason, it is easy to obtain a first 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.

[0088] The terminal unit represented by Equation (a1) is Equation (a2) below:

[0089] *-Y 2 -Y 1 -** … (a2)

[0090] By interposing a linker represented by, it is bonded to the main chain of the terminal maleimide modified polyphenylene ether resin (A).

[0091] The bonding hand on the ** side of the above linker is bonded to an oxygen atom originating from a hydroxyl group at the end of the molecular chain of an unmodified polyphenylene ether resin (A') that gives the end maleimide-modified polyphenylene ether resin (A). Meanwhile, the bonding hand on the * side of the linker is bonded to a terminal group represented by formula (a1).

[0092] In equation (a2), Y 1 It is a single bond, or a carbonyl group. Y 2is 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.

[0093] In equation (a2), 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.

[0094] In short, Y in equation (a2) 1 In the case of this carbonyl group, the linker represented by formula (a2) is preferably a group represented by the following formulas (a2-1) to (a2-3).

[0095] *-Y 4 -CO-** … (a2-1)

[0096] *-Y 4 -O-CO-** … (a2-2)

[0097] *-Y 4 -NH-CO-** … (a2-3)

[0098] Y 4 The organic group of 2 as is Y 3 The 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.

[0099] Y 4 In the case of the end maleimide modified polyphenylene ether resin (A), hydrocarbon groups are preferred because the compound used for end modification is easy to obtain or manufacture, or the desired end modification is easy.

[0100] 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.

[0101] The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Aliphatic hydrocarbon groups are preferred as hydrocarbon groups due to their flexibility compared to rigid aromatic hydrocarbon groups.

[0102] 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.

[0103] 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.

[0104] In equation (a2), 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 2It is a carbon atom that constitutes the entire structure or partial structure of an aliphatic hydrocarbon group in an organic group.

[0105] In equation (a2), 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 an unmodified polyphenylene ether resin (A') that gives the terminal maleimide-modified polyphenylene ether resin (A) to a terminal group represented by formula (a1). Y 1 Y in the case of this single bond 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.

[0106] 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.

[0107] Y 1 In the case of this single bond, Y 2 The divalent 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-).

[0108] Y 1 In the case of this single bond, Y 2Preferred 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-).

[0109] 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.

[0110] The method of modifying an unmodified polyphenylene ether resin (A') by introducing a terminal group represented by formula (a1) to the molecular chain end is not particularly limited.

[0111] To perform this modification, an unmodified polyphenylene ether resin (A') having phenolic hydroxyl terminals is preferably used.

[0112] The unmodified polyphenylene ether resin (A') may be a resin having at least one phenolic hydroxyl group terminal. The unmodified polyphenylene ether resin (A') 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.

[0113] In addition, when the unmodified polyphenylene ether resin (A') has a phenolic hydroxyl group at the end, the unmodified polyphenylene ether resin (A') may additionally have a phenolic hydroxyl group on the phenylene group included in the main chain.

[0114] 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. The method of producing the unmodified polyphenylene ether resin (A') is not particularly limited, but it is preferable that the unmodified polyphenylene ether resin (A') be produced according to a known method or the typical method described above.

[0115] The phenylene group included in the main chain of the terminal maleimide-modified polyphenylene ether resin (A) may have 1 to 4 substituents. Accordingly, the phenylene group included in the main chain of the unmodified polyphenylene ether resin (A') may also have 1 to 4 substituents.

[0116] 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.

[0117] 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.

[0118] Examples of unmodified polyphenylene ether resins (A') include homopolymers of phenols or copolymers of two or more phenols.

[0119] The unmodified polyphenylene ether resin (A') may be a polymer obtained by polymerizing only monovalent phenol, or a polymer obtained by copolymerizing monovalent phenol with polyvalent phenol such as divalent phenol or trivalent phenol.

[0120] A polymer consisting solely of 1 phenol 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.

[0121] 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. Also, 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.

[0122] 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).

[0123] 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.

[0124] 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.

[0125] 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.

[0126] As for the unmodified polyphenylene ether resin (A'), 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, a copolymer of 3,3',5,5'-tetramethylbisphenol A, and a copolymer of 2,6-dichlorophenol are preferred, and a copolymer of 3,3',5,5'-tetramethylbisphenol A, which is a copolymer of 2,6-dimethylphenol is more preferred.

[0127] The method of modifying an unmodified polyphenylene ether resin (A') to introduce a terminal group represented by formula (a1) at the end is not particularly limited.

[0128] For example, Y in equation (a2) 1 This is a carbonyl group, and the linker represented by formula (a2) is the following formula (a2-1):

[0129] *-Y 4 -CO-** … (a2-1)

[0130] In the case of a cause represented by , MIG-Y 4 By condensing the carboxylic acid represented by -CO-OH and the phenolic hydroxyl group of the unmodified polyphenylene ether resin (A') using a condensation agent such as carbonyldiimidazole or a carbodiimide-based compound such as N,N'-diisopropylcarbodiimide, the terminal phenolic hydroxyl group of the unmodified polyphenylene ether resin (A') is modified to -O-CO-Y 4It can be converted into a group represented by -MIG. Also, MIG is a terminal group represented by equation (a1).

[0131] Also, MIG-Y 4 By reacting a carboxylic acid halide represented as -CO-Hal with the phenolic hydroxyl group of the unmodified polyphenylene ether resin (A'), the terminal phenolic hydroxyl group of the unmodified polyphenylene ether resin (A') is 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.

[0132] Y in equation (a2) 1 This is a carbonyl group, and the linker represented by formula (a2) is the following formula (a2-2):

[0133] *-Y 4 -O-CO-** … (a2-2)

[0134] In the case of the group represented by , the phenolic hydroxyl groups of the unmodified polyphenylene ether resin (A') and an excess amount of MIG-Y relative 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 (A') are -O-CO-OY 4 It can be converted into a unit represented by -MIG.

[0135] Y in equation (a2) 1 This is a carbonyl group, and the linker represented by formula (a2-3) is the following formula (a2-3):

[0136] *-Y 4 -NH-CO-** … (a2-3)

[0137] In the case of a group represented as such, the phenolic hydroxyl groups of the unmodified polyphenylene ether resin (A') are MIG-Y 4By reacting with an isocyanate represented by -NCO, the terminal phenolic hydroxyl groups of the unmodified polyphenylene ether resin (A') are modified to -O-CO-NH-Y 4 It can be converted into a unit represented by -MIG.

[0138] Y in equation (a2) 1 In the case of this single bond, the phenolic hydroxyl group of the unmodified polyphenylene ether resin (A') 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 (A') are modified to -OY 2 It can be converted into a unit represented by -MIG.

[0139] 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).

[0140] 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.

[0141] When preparing a terminal maleimide modified polyphenylene ether resin (A) using an unmodified polyphenylene ether resin (A'), 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 (A'), or a group including a terminal group represented by formula (a1) may be introduced to all of the phenolic hydroxyl groups.

[0142] The molecular weight of the terminal maleimide-modified polyphenylene ether resin (A) 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 2,000 or more, more preferably 2,500 or more, and even more preferably 3,000 or more. The molecular weight of the resin (A) is preferably 100,000 or less, more preferably 80,000 or less, even more preferably 50,000 or less, and even more preferably 10,000 or less as the mass average molecular weight (Mw).

[0143] In this specification, the mass average molecular weight (Mw) is a measured value by polystyrene conversion of gel permeation chromatography (GPC).

[0144] In this way, the terminal maleimide modified polyphenylene ether resin (A) having the terminal group represented by formula (a1) at a specific position 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 terminal maleimide modified polyphenylene ether resin (A) provides an insulating film with low dielectric constant, 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.

[0145] The first curable composition comprising a terminal maleimide modified polyphenylene ether resin (A) has excellent film-forming properties in the coating method. For this reason, when a film is formed by the 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 the coating method, which is an easy method.

[0146] The terminal maleimide modified polyphenylene ether resin (A) has excellent solvent solubility. Therefore, the first curable composition containing the terminal maleimide modified polyphenylene ether resin (A) is applicable to a developing process using the solvent as a negative type composition.

[0147] In particular, the terminal maleimide modified polyphenylene ether resin (A) may be soluble in an alkaline aqueous solution, depending on its structure. For example, the terminal maleimide modified polyphenylene ether resin (A) may have alkali-soluble groups such as carboxyl groups or phenolic hydroxyl groups. A first curable composition comprising such an alkali-soluble terminal maleimide modified polyphenylene ether resin (A) can be applied to an alkali development process as a negative type composition.

[0148] An insulating film of a desired pattern shape can be formed by applying position-selective exposure and the above-described development process to a coating film comprising a first curable composition including a terminal maleimide modified polyphenylene ether resin (A).

[0149] The content of the terminal maleimide modified polyphenylene ether resin (A) in the first curable composition is not particularly limited. The content of the terminal maleimide modified polyphenylene ether resin (A) is preferably 5 mass% or more and 100 mass% or less with respect to the total solid content of the first curable composition.

[0150] [Radical polymerizable compound (B)]

[0151] The first curable composition may additionally include a radical polymerizable compound (B). Of course, the first curable composition may not include the radical polymerizable compound (B).

[0152] Radical polymerizable compound (B) is a radical polymerizable compound other than terminal maleimide modified polyphenylene ether resin (A).

[0153] The radical polymerizable compound (B) may be a compound having an unsaturated double bond, such as styrene, styrene polymer, acrylonitrile, (meth)acrylic acid, or (meth)acrylic acid ester, but it is preferable that it be a radical polymerizable compound having a group represented by the above formula (a1).

[0154] As for the radical polymerizable compound having the group represented by the above formula (a1), a polyfunctional maleimide compound having two or more groups represented by the formula (a1) is preferred, and a bismaleimide compound having two amino groups of an aromatic diamine or an aliphatic diamine substituted with the group represented by the formula (a1) is preferred.

[0155] 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.

[0156] Specific examples of aliphatic diamines include pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, 2,3,3-trimethylpentane-1,5-diamine, etc.

[0157] Radical polymerizable compounds having the group represented by the above formula (a1) 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.).

[0158] [Chemical Formula 7]

[0159]

[0160] As radical polymerizable compounds other than the maleimide compound mentioned above, various radical polymerizable compounds conventionally incorporated into radical polymerizable compositions may be used without particular limitation. Specific examples of radical polymerizable compounds other than the maleimide compound include the following compounds.

[0161] 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.

[0162] 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)acryloxypolyepoxyphenyl)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 product of 2-hydroxyethyl (meth)acrylate with trimethylhexamethylene diisocyanate and hexamethylene diisocyanate, etc., 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.

[0163] The content of the radical polymerizable compound (B) in the first 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 terminal maleimide modified polyphenylene ether resin (A) and the radical polymerizable compound (B).

[0164] [Radical generator (C)]

[0165] The first curable composition comprises a radical generator (C). The radical generator (C) may be a photoradical generator (C1) or a thermal radical generator (C2), or a combination of a photoradical generator (C1) and a thermal radical generator (C2).

[0166] 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).

[0167] Specific examples of photoradical generators (C1) include 1-hydroxycyclohexylphenyl ketone, 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.

[0168] 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 peroxyisobutylate and Organic peroxides of {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).

[0169] The content of the radical generator (C) in the first curable composition is not particularly limited, but with respect to 100 parts by mass of the total mass of the terminal maleimide modified polyphenylene ether resin (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.

[0170] <Organic Solvent (S)>

[0171] The first curable composition typically comprises 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 photosensitive compositions.

[0172] 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 organic solvents such as heteroatom-containing aromatic compounds (e.g., anisole), aromatic hydrocarbons (e.g., toluene, xylene); etc. These may be used individually or in a mixture of two or more types.

[0173] 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 first curable composition is 30 mass% or more and 70 mass% or less.

[0174] [Other Additives]

[0175] The first curable composition may additionally contain a maleimide curing agent (E) to improve curability, and may additionally contain a surfactant to improve coating properties, anti-foaming properties, leveling properties, etc.

[0176] Examples of maleimide curing agents include diamines; low-polarity polyfunctional allylphenol resins (e.g., FATC (manufactured by Gun-ei Chemical Industry Co., Ltd.)), low-polarity allyletherphenol resins (e.g., FTC-AE (manufactured by Gun-ei Chemical Industry Co., Ltd.)), allyl compounds such as allyl ethers; 1-propenyl compounds having a 1-propenyl group such as propenified biphenylene resins (e.g., BPN (manufactured by Gun-ei Chemical Industry Co., Ltd.)), and benzoxazine compounds.

[0177] As surfactants, for example, fluorine-based surfactants or silicone-based surfactants are preferably used.

[0178] 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.

[0179] 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.

[0180] Commercially available silicone surfactants may be used as silicone surfactants. Specific examples of commercially available silicone surfactants include Painted 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 Big Chem).

[0181] The first curable composition may contain an antioxidant. The antioxidant is not particularly limited and conventionally known antioxidants may be used, such as hindered phenol-based antioxidants (e.g., Irganox 1010 (manufactured by BASF)), hindered amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, etc.

[0182] The first curable composition may contain a polymerization inhibitor to appropriately prevent polymerization during the reaction. The polymerization inhibitor is not particularly limited and conventionally known polymerization inhibitors may be used, such as mesoquinone, hydroquinone, methylhydroquinone, p-methoxyphenol, pyrogallol, tert-butylcatechol, phenothiazine, etc.

[0183] The first curable composition may contain an adhesion enhancer to improve the adhesion between a metal wiring or a substrate for an electrical or electronic device having metal wiring and an insulating film formed using the first curable composition. The adhesion enhancer is not particularly limited and may use conventionally known adhesion enhancers, such as benzotriazole.

[0184] [Method for preparing the first curable composition]

[0185] The first 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.

[0186] <Second Curable Composition>

[0187] The second curable composition comprises a terminal maleimide-modified polyphenylene ether resin (A) and a radical generator (C), identical to the first curable composition. The use of the second curable composition is not particularly limited. The second curable composition can be applied to various applications where conventionally known negative-type photosensitive resin compositions are applied. For the use of the second curable composition, an insulating film forming application identical to that of the first curable composition is preferred.

[0188] The terminal maleimide modified polyphenylene ether resin (A) used in the second curable composition is the same as the terminal maleimide modified polyphenylene ether resin described for the first curable resin composition, except that the linker existing between the terminal group represented by formula (a1) and the oxygen atom derived from the phenolic hydroxyl group of the unmodified polyphenylene ether resin (A') is not particularly limited.

[0189] Also, the radical generator (C) used in the second curable composition is the aforementioned photoradical generator (C1).

[0190] Any component that may be included in the second curable composition is the same as any component that may be included in the first curable composition. Also, the content of each component in the second curable composition is the same as the content of each component in the first curable composition.

[0191] ≪Method for Forming an Insulating Film≫

[0192] An insulating film is formed using the first curable composition or the second curable composition. Hereinafter, the first curable composition and the second curable composition will be referred to collectively as "curable composition."

[0193] The method for forming an insulating film is,

[0194] A coating process for forming a coating film by applying a curable composition to an insulating film formation site, and

[0195] It includes a curing process for curing the coating film.

[0196] 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.

[0197] 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.

[0198] 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.

[0199] 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.

[0200] 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 70°C or higher and 200°C or lower, preferably 80°C or higher and 150°C or lower, and 2 minutes or more and 120 minutes or less.

[0201] 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 may be performed selectively by a specific method, such as exposing the active light or radiation through a mask of a predetermined pattern.

[0202] By exposure to light, a polymerizing component, such as a resin (A) or a radical polymerizable compound (B), polymerizes to form an insulating film. As a result, an insulating film is formed on a substrate for an electrical or electronic device having metal wiring, for example.

[0203] 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 / ㎠ or more and 10,000 mJ / ㎠ or less. In addition, the radiation may include light that activates a radical generator (C) to generate radicals.

[0204] 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 terminal maleimide modified polyphenylene ether resin (A) has an alkali-soluble group such as a carboxyl group or a phenolic hydroxyl group, development with an alkaline aqueous solution is possible.

[0205] 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.

[0206] 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.

[0207] 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.

[0208] 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.

[0209] In addition, the above describes an example in which an insulating film is formed by polymerizing a polymerizing component resin (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 polymerizing component resin (A) or the radical polymerizable compound (B) by heating.

[0210] 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 5G communication band candidate frequencies of 3 GHz to 30 GHz or millimeter wave band frequencies of 30 GHz to 300 GHz. In addition, since the formed insulating film has excellent heat resistance, it is suitable for applications where additional components, such as wiring, are formed by heating after the insulating film is formed.

[0211] Examples

[0212] The present invention will be explained in more detail below by way of examples, but the present invention is not limited to these examples.

[0213] [Preparation Example 1]

[0214] As an unmodified polyphenylene ether resin (A'), a polyphenylene ether resin having phenolic hydroxyl terminals of the following structure (SA90, manufactured by SABIC Innovative Plastics) was used.

[0215] [Chemical Formula 8]

[0216]

[0217] 166 parts by mass of unmodified polyphenylene ether resin (A') 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.

[0218] [Chemical Formula 9]

[0219]

[0220] 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 terminal maleimide modified polyphenylene ether resin P1 (resin P1), in which the phenolic hydroxyl groups at both ends of the unmodified polyphenylene ether resin (A') were modified into groups of the following formula. The mass average molecular weight (Mw) of the terminal maleimide modified polyphenylene ether resin P1, measured by gel permeation chromatography (GPC), was 7000 in polystyrene equivalent.

[0221] [Chemical Formula 10]

[0222]

[0223] For the obtained terminal maleimide modified polyphenylene ether resin P1 and polyphenylene ether resin (SA90), chloroform was used as a measuring solvent 1 H NMR measurements were performed. 1 The results of the H NMR measurement are shown in Fig. 1. In Fig. 1, the upper spectrum is the measurement result of polyphenylene ether resin (SA90), and the lower spectrum is the measurement result of terminal maleimide modified polyphenylene ether resin P1.

[0224] According to Figure 1, the peak originating from the 6.7 ppm maleimide backbone is present in the lower spectrum but not in the upper spectrum, so it can be seen that the terminal maleimide modified polyphenylene ether resin P1 is a resin that has undergone the desired terminal maleimide modification.

[0225] [Jojeye 2]

[0226] A denaturation reaction of the terminal phenolic hydroxyl group was carried out in the same manner as in Preparation Example 1, except that the carboxylic acid having a maleimide group was changed to 43.6 parts by mass of a compound having the following structure.

[0227] [Chemical Formula 11]

[0228]

[0229] 126 parts by mass of terminal maleimide modified polyphenylene ether resin P2 (resin P2) were obtained, in which the phenolic hydroxyl groups at both ends of an unmodified polyphenylene ether resin (A') were modified into groups of the following formula. The mass average molecular weight (Mw) of the terminal maleimide modified polyphenylene ether resin P2, measured by gel permeation chromatography (GPC), was 7000 in polystyrene equivalent.

[0230] [Chemical Formula 12]

[0231]

[0232] [Joje-ye 3]

[0233] A denaturation reaction of the terminal phenolic hydroxyl group was carried out in the same manner as in Preparation Example 1, except that the carboxylic acid having a maleimide group was changed to 57.0 parts by mass of a compound having the following structure.

[0234] [Chemical Formula 13]

[0235]

[0236] 140 parts by mass of terminal maleimide modified polyphenylene ether resin P3 (resin P3) were obtained, in which the phenolic hydroxyl groups at both ends of an unmodified polyphenylene ether resin (A') were modified into groups of the following formula. The mass average molecular weight (Mw) of the terminal maleimide modified polyphenylene ether resin P3, measured by gel permeation chromatography (GPC), was 7000 in polystyrene equivalent.

[0237] [Chemical Formula 14]

[0238]

[0239] <Preparation of Curable Composition>

[0240] [Examples 1 to 9, and Comparative Examples 1 to 7]

[0241] In Examples 1 to 9, the resins P1 to P3 were used as resin (A).

[0242] In Examples 1 to 9 and Comparative Examples 1 to 7, the following B1 to B5 and B6: SA9000 (manufactured by SABIC Innovative Plastics, a modified polyphenylene ether in which the terminal hydroxyl groups of a polyphenylene ether are modified to methacrylate groups) were used as radical polymerizable compounds (B). Additionally, B1 is BMI-689 and B2 is BMI-3000 (both manufactured by Designer Molecules).

[0243] [Chemical Formula 15]

[0244]

[0245] [Chemical Formula 16]

[0246]

[0247] In Examples 1 to 9 and Comparative Examples 1 to 7, the following C1 to C4 were used as radical generators (C).

[0248] C1 : Irgacure OXE01 (Manufactured by BASF)

[0249] C2: Irgacure OXE02 (Manufactured by BASF)

[0250] C3: Omnirad 819 (manufactured by IGM Resins BV)

[0251] C4: Perhexyl D (manufactured by Nichiyu)

[0252] In Examples 1 to 9 and Comparative Examples 1 to 7, the following D1 to D3 and a surfactant (BYK310, manufactured by Big Chem Co.) were used as additives.

[0253] D1: Irganox 1010 (Manufactured by BASF)

[0254] D2: Mesoquinone

[0255] D3 : Benzotriazole

[0256] Curable compositions of each example and comparative example were obtained by dissolving a terminal maleimide modified polyphenylene ether resin (resin (A)) and / or a radical polymerizable compound (B), a radical generator (C), an additive, and 0.05 parts by mass of a surfactant (BYK310, manufactured by Big 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%.

[0257] <Evaluation>

[0258] Using the obtained curable composition, film formation properties, photolithography properties, 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.

[0259] [Tabernacle-like and Photolithographic Characteristics]

[0260] 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 with 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).

[0261] 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).

[0262] The surface of the coating film prior to pre-baking was observed using a scanning electron microscope, and the film formation properties were evaluated. Specifically, ○ was used when no cracks or / or crystals were observed on the pattern surface, there was no tack (stickiness) on the pattern, and the contained components were in use, making it transparent. Additionally, the evaluation was conducted as a when cracks were observed on the pattern surface, b when crystals were observed on the pattern surface, c when there was tack (stickiness) on the pattern surface, and d when the contained components were not in use and the film was opaque.

[0263] In addition, the surface and cross-section of the obtained pattern (insulating film) were observed using a scanning electron microscope, and photolithographic characteristics were evaluated. Specifically, within the exposure amount range described above, the evaluation was performed by assigning ○ when a condition in which an aperture of 30 μm in diameter is formed existed, and × when a condition in which an aperture of 30 μm in diameter is formed does not exist.

[0264] In addition, Comparative Example 1 was not evaluated for dielectric constant, dielectric loss tangent, or heat resistance because it had a tag and could not form a pattern (insulating film).

[0265] In addition, Comparative Examples 3 and 4 were not evaluated for photolithography properties, dielectric constant, dielectric loss tangent, and heat resistance because cracks or crystals occurred in the coating film prior to prebaking.

[0266] [Permittivity and Dielectric Loss Tangent]

[0267] 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 dose 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.

[0268] 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.

[0269] The permittivity was evaluated by marking ○ when the permittivity value was less than 3.00 and × when it was 3.00 or greater.

[0270] The genetic loss tangent was evaluated by marking ○ when the genetic loss tangent was less than 0.01 and × when it was 0.01 or greater.

[0271] [Heat resistance]

[0272] 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.

[0273] Heat resistance was evaluated by marking ○ when Tg was 150 ℃ or higher and × when Tg was less than 150 ℃.

[0274]

[0275]

[0276] According to Examples 1 to 9, it can be seen that a curable composition comprising a terminal maleimide modified polyphenylene ether resin (A) having a group represented by formula (a1) at the end of the molecular chain and a radical generator (C) can form an insulating film with low dielectric constant and dielectric loss tangent and excellent heat resistance, and also has excellent film formation properties. In addition, in the compositions of Examples 1 to 9, the terminal maleimide modified polyphenylene ether resin (A) was dissolved in PGMEA. In addition, according to Examples 1 to 9, it can be seen that the photolithography properties are also excellent.

[0277] Meanwhile, according to Comparative Examples 1 to 7, it can be seen that when the curable composition does not contain the terminal maleimide modified polyphenylene ether resin (A), it is difficult to achieve both the formation of an insulating film with low dielectric constant and dielectric loss tangent and excellent heat resistance and good film formation properties.

[0278] [Examples 10 to 12]

[0279] In Example 10, a curable composition with the same components and amounts as in Example 1 was prepared, as shown in Table 3, except that anisole was used instead of PGMEA as the organic solvent, and the obtained curable composition was evaluated in the same way as in Example 1.

[0280] In Examples 11 and 12, FATC and FTC-AE (both manufactured by Gun-E Chemical Industry Co., Ltd.) were mixed in the amounts shown in Table 3 as the maleimide curing agent (E) that is an additive in Example 10 to prepare a curable composition, and the obtained curable composition was evaluated in the same way as in Example 1. In addition, FATC is represented as E1 below, and FTC-AE is represented as E2 below.

[0281] [Chemical Formula 17]

[0282]

[0283]

[0284] In the composition of Example 10, a terminal maleimide-modified polyphenylene ether resin (A) was dissolved in anisole. Furthermore, it was found that in the composition of Example 10, just like in Example 1, an insulating film with low dielectric constant and dielectric loss tangent, excellent heat resistance, and excellent photolithography properties could be formed, and the film formation properties were also excellent. In addition, the compositions of Examples 11 and 12, which incorporated a maleimide curing agent (E) as an additive, showed the same results as the composition of Example 10.

Claims

Claim 1 A curable composition comprising a terminal maleimide modified polyphenylene ether resin (A) and a radical generator (C), wherein the terminal maleimide modified polyphenylene ether resin (A) is of the following formula (a1): Having a terminal group represented by at the end of the molecular chain, and in the above 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 phenylene group included in the main chain of the terminal maleimide-modified polyphenylene ether resin (A) may have 1 to 4 substituents, and the terminal group is of the following formula (a2): *-Y 2 -Y 1 -** ... (a2) interposed with a linker, which is bonded to the main chain of the terminal maleimide-modified polyphenylene ether resin (A), wherein 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 (A') that gives the terminal maleimide-modified polyphenylene ether resin (A), and the bonding hand on the * side of the linker is bonded to the terminal group, and in the formula (a2), Y 1 Silver is a carbonyl group, and Y 2 A curable composition used for forming an insulating film, which is butane-1,4-diyl group, cyclohexane-1,4-diyl group, or cyclohexane-1,3-diyl group. Claim 2 A curable composition according to claim 1, further comprising a radical polymerizable compound (B) which is a radical polymerizable compound other than the terminal maleimide modified polyphenylene ether resin (A). Claim 3 A curable composition according to claim 2, wherein the radical polymerizable compound (B) comprises a radical polymerizable compound having a group represented by the formula (a1). Claim 4 A cured product of the curable composition described in claim 1. Claim 5 A method for forming an insulating film, comprising: a coating process for forming a coating film by applying a curable composition described in claim 1 to an insulating film formation site, and a curing process for curing the coating film. Claim 6 A method for forming an insulating film according to claim 5, 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 7 A method for forming an insulating film according to claim 6, 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 8 delete Claim 9 delete Claim 10 delete Claim 11 delete Claim 12 delete Claim 13 delete Claim 14 delete

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