Resin composition, cured product, laminate, and electronic component

Abstract

To provide a resin composition which gives a cured product excellent in a low dielectric constant, a low dielectric loss tangent, tracking resistance and a process margin, and is excellent in impregnability into a substrate.SOLUTION: The composition comprises a polymer (A) having at least one group selected from the group consisting of a (meth)acryloyloxy group and a group represented by CH2 = CR - *, a compound (B), and a solvent (C), wherein R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. *Represents a bonding site with another structure, the compound (B) is a hindered amine compound (B1) having no electron-withdrawing group other than a nitroxy radical group and a hindered amine compound (B2) having an electron-withdrawing group other than a nitroxy radical group, and a content ratio of the hindered amine compound (B1) is 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the polymer (A).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin composition, a cured product, a laminate, and an electronic component. [Background technology]

[0002] In recent years, in the field of information and communications, the signal bandwidth of information and communications equipment has been increasing in frequency in order to achieve high-speed, large-capacity transmission. To accommodate this increase in frequency, there is an increasing demand for low-dielectric and low-dielectric-tangent materials for the insulators used in printed wiring boards and semiconductor packages.

[0003] As materials that can accommodate this trend toward higher frequencies, polyolefin resin, styrene resin, fluororesin, polyphenylene ether resin, vinylbenzyl ether resin, or compositions using polyphenylene ether resin have been proposed (see, for example, Patent Documents 1 to 6). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 7-188362 [Patent Document 2] Japanese Patent Application Laid-Open No. 2004-83680 [Patent Document 3] Patent No. 3414556 [Patent Document 4] Japanese Patent Application Laid-Open No. 2003-306591 [Patent Document 5] Patent No. 5649773 [Patent Document 6] Japanese Patent Application Laid-Open No. 2017-200997 Summary of the Invention [Problem to be solved by the invention]

[0005] However, although conventional materials such as the compositions described in Patent Documents 1 to 6 are somewhat excellent in terms of low dielectric constant and low dielectric dissipation factor, they do not necessarily satisfy all of the requirements for properties necessary for electronic materials, such as heat resistance, chemical resistance, and adhesiveness. For example, compositions using polyphenylene ether resins and fluororesins have low dielectric constants, low dielectric dissipation factors, and excellent heat resistance, but do not have sufficient adhesion to low-roughening copper foils.Furthermore, the composition described in Patent Document 6 has room for improvement in terms of chemical resistance and low dielectric properties.

[0006] The problem to be solved by one embodiment of the present invention is to provide a resin composition which provides a cured product with a low dielectric constant, a low dielectric loss tangent, excellent tracking resistance and process margin, and excellent impregnation ability into substrates. [Means for solving the problem]

[0007] The means for solving the above problems include the following aspects. <1> a polymer (A) having at least one group selected from the group consisting of a (meth)acryloyloxy group and a group represented by CH═CR—; Compound (B), a solvent (C); Contains wherein R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and * represents a bonding site to another structure; the compound (B) is a hindered amine compound (B1) having no electron-withdrawing group other than a nitroxy radical group, and a hindered amine compound (B2) having an electron-withdrawing group other than a nitroxy radical group, The resin composition contains the hindered amine compound (B1) in an amount of 0.1 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the polymer (A). <2> The polymer (A) is a polymer having a repeating unit represented by the following formula (1): <1> The resin composition according to claim 1.

[0008] [ka]

[0009] In formula (1), each X is independently -O-, -S-, or -N(R 3 )-, wherein R 3 represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, or a group in which a portion of such a hydrocarbon group or halogenated hydrocarbon group is substituted with at least one atom selected from an oxygen atom and a sulfur atom, and R 1 is a divalent organic group, and R 2 is a divalent unsubstituted or substituted nitrogen-containing heteroaromatic ring. <3> The polymer (A) is a polymer having a group represented by the following formula (a) at its terminal: <1> or <2> The resin composition according to claim 1.

[0010] [ka]

[0011] In formula (a), Y represents a group containing an ethylenically unsaturated double bond having 3 to 50 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an unsubstituted or substituted aliphatic hydrocarbon group having 6 to 50 carbon atoms, or an unsubstituted nitrogen-containing heteroaromatic ring, and when the aromatic hydrocarbon group or the aliphatic hydrocarbon group has a substituent, the substituent is a group other than a hydroxy group. <4> further contains a curable compound (D), and the content ratio of the hindered amine compound (B1) is 0.01 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the total content of the polymer (A) and the curable compound (D); <1> ~ <3> The resin composition according to any one of the above. <5> The hindered amine compound (B1) is a compound represented by the following formula (B1-1): <1> ~ <4> The resin composition according to any one of the above.

[0012] [ka] <6> The hindered amine compound (B2) is a compound represented by the following formula (B2-1): <1> ~ <5> The resin composition according to any one of the above.

[0013] [ka]

[0014] In formula (B2-1), R B21 represents an electron-withdrawing group other than a nitroxy radical group, and n B21 represents an integer from 1 to 6. <7> <1> ~ <6> A cured product, which is a cured product of the resin composition described in any one of the above. <8> <7> A laminate comprising a layer made of the cured product according to claim 1. <9> <8> An electronic component having the laminate according to claim 1. [Effects of the Invention]

[0015] According to one embodiment of the present invention, there is provided a resin composition which provides a cured product with a low dielectric constant, a low dielectric loss tangent, excellent tracking resistance and process margin, and excellent impregnation ability into substrates. DETAILED DESCRIPTION OF THE INVENTION

[0016] Preferred embodiments of the present invention will be described in detail below. It should be understood that the present invention is not limited to the embodiments described below, but also includes various modifications that are implemented within the scope of the present invention. In this specification, a numerical range stated using "to" means that the numerical values ​​before and after "to" are included as the lower limit and upper limit. In this specification, the term (meth)acryloyloxy is used as a concept that includes both acryloyloxy and methacryloyloxy. When a plurality of components are present in the composition, the amount of each component in the composition means the total amount of the plurality of substances present in the composition, unless otherwise specified. Hereinafter, a resin composition, a cured product, a laminate, and an electronic component according to one embodiment of the present invention will be described in detail.

[0017] [Resin composition] The resin composition according to the present invention comprises a polymer (A) having at least one group selected from the group consisting of a (meth)acryloyloxy group and a group represented by CH═CR—*, a compound (B), a solvent (C), and Contains wherein R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and * represents a bonding site to another structure; the compound (B) is a hindered amine compound (B1) having no electron-withdrawing group other than a nitroxy radical group, and a hindered amine compound (B2) having an electron-withdrawing group other than a nitroxy radical group, The content of the hindered amine compound (B1) is 0.1 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the polymer (A).

[0018] <<Polymer (A)>> The polymer (A) has at least one group selected from the group consisting of a (meth)acryloyloxy group and a group represented by CH2=CR-*. The above R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and * represents a bonding site to another structure. From the viewpoint of excellent polymerization reactivity, R is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, still more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

[0019] Examples of groups containing a group represented by CH2=CR-* include an allyl group, a vinyl group, an isopropenyl group, a 1-buten-2-yl group, a 1-penten-2-yl group, a vinylphenyl group, and an allylphenyl group. When the group represented by CH2=CR-* is present at the main chain terminal of the polymer (A), examples of the terminal structure containing the group represented by CH2=CR-* include an allyloxy group, a vinylphenyloxy group, an allylphenyloxy group, an isopropenylphenyloxy group, and a vinylphenylmethyloxy group.

[0020] * preferably represents a bonding site to a carbon atom in an aliphatic hydrocarbon structure or a carbon atom that is a ring member of an aromatic hydrocarbon ring. The aliphatic hydrocarbon structure is preferably a saturated aliphatic hydrocarbon structure, such as a methylene group or an alkanediyl group having 2 to 6 carbon atoms. The aromatic hydrocarbon ring is not particularly limited and may have any structure of an unsubstituted or substituted aromatic hydrocarbon ring. The aromatic hydrocarbon ring is preferably an aromatic hydrocarbon ring having 6 to 30 carbon atoms, more preferably a benzene ring, a naphthalene ring, or an anthracene ring, and particularly preferably a benzene ring or a naphthalene ring. In this specification, the term "bonding site to a certain structure X" refers to a site that directly bonds to structure X without a linking group.

[0021] When the aromatic hydrocarbon ring has a substituent, examples of the substituent include a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, a nitro group, a cyano group, a carboxy group, a sulfonic acid group, a phosphonic acid group, a phosphate group, a hydroxy group, a primary to tertiary amino group, a salt of a carboxy group, a salt of a sulfonic acid group, a salt of a phosphonic acid group, a salt of a phosphate group, a salt of a hydroxy group, or a salt of a primary to tertiary amino group. Specific examples of the halogen atom, the monovalent hydrocarbon group having 1 to 20 carbon atoms, the monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, the alkoxy group having 1 to 20 carbon atoms, the alkylthio group having 1 to 20 carbon atoms, the nitro group, the cyano group, the carboxy group, the sulfonic acid group, the phosphonic acid group, the phosphoric acid group, the hydroxy group, the primary to tertiary amino groups, the salts of the carboxy group, the salts of the sulfonic acid group, the salts of the phosphonic acid group, the salts of the phosphoric acid group, the salts of the hydroxy group, and the salts of the primary to tertiary amino groups include Ar1 and A in formula (2-1) described later. In the aromatic hydrocarbon group represented by r2, it has the same meaning as a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, a nitro group, a cyano group, a carboxy group, a sulfonic acid group, a phosphonic acid group, a phosphate group, a hydroxy group, a primary to tertiary amino group, a salt of a carboxy group, a salt of a sulfonic acid group, a salt of a phosphonic acid group, a salt of a phosphate group, a salt of a hydroxy group, and a salt of a primary to tertiary amino group.

[0022] From the viewpoint of polymerization reactivity, the number of substituents is preferably 0 to 2, and more preferably 0 or 1. An embodiment in which the number of the substituents is 0 is also one of the preferred embodiments of the present invention.

[0023] Suitable examples of the polymer (A) include polyphenylene ether polymers, polyfunctional vinyl aromatic copolymers, and heteroaromatic-aromatic ether polymers having at least one group selected from the group containing a (meth)acryloyloxy group and the group represented by CH═CR-* (where R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and * represents a bonding site to another structure) at the end of the main chain or in a side chain of the polymer. Hereinafter, these may be abbreviated as "modified polyphenylene ether polymer," "modified polyfunctional vinyl aromatic copolymer," and "modified heteroaromatic-aromatic ether polymer," respectively.

[0024] These polymers (A) have at least one group selected from the group consisting of a (meth)acryloyloxy group and a group represented by CH═CR-*, and therefore have excellent low dielectric constants and low dielectric dissipation factors. From the viewpoint of achieving even better low dielectric constants and low dielectric dissipation factors, the polymer (A) is preferably at least one resin selected from the group consisting of a polyphenylene ether polymer, a polyfunctional vinyl aromatic copolymer, and a heteroaromatic-aromatic ether polymer.

[0025] The polymer (A) is preferably a polymer having a repeating unit represented by the following formula (1).

[0026] [ka]

[0027] In formula (1), each X is independently -O-, -S-, or -N(R 3 )-, wherein R 3 represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, or a group in which a portion of the hydrocarbon group or halogenated hydrocarbon group is substituted with at least one atom selected from an oxygen atom and a sulfur atom, and R 1 is a divalent organic group, and R 2 is a divalent unsubstituted or substituted nitrogen-containing heteroaromatic ring.

[0028] R 1 The divalent organic group represented by the formula (2-1) preferably contains a group represented by the formula (2-1) below.

[0029] [ka]

[0030] In formula (2-1), Ar1 and Ar2 each independently represent an unsubstituted or substituted aromatic hydrocarbon group. L is a single bond, -O-, -S-, -N(R 8)-, -C(O)-, -C(O)-O-, -C(O)-NH-, -S(O)-, -S(O)2-, -P(O)-, or a divalent organic group. 8 is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms. y is an integer of 0 to 5. When y is 2 or more, the plurality of Ar1's and L's may be the same or different. R 6 and R 7 are each independently a single bond, a methylene group, or an alkanediyl group having 2 to 4 carbon atoms.

[0031] The aromatic hydrocarbon groups represented by Ar1 and Ar2 are each independently preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably a phenylene group, a naphthalenediyl group, or an anthracenediyl group, and particularly preferably a phenylene group or a naphthalenediyl group.

[0032] The aromatic hydrocarbon groups represented by Ar1 and Ar2 may each have 1 to 8 substituents. The number of substituents that the aromatic hydrocarbon groups represented by Ar1 and Ar2 each have is preferably 0 to 8, more preferably 0 to 4, and even more preferably 0 to 2, from the viewpoint of enabling the synthesis of polymer (A) with good polymerization reactivity.

[0033] The substituents in Ar1 and Ar2 are not particularly limited, and examples thereof include an allyl group, a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, a nitro group, a cyano group, a carboxy group, a sulfonic acid group, a phosphonic acid group, a phosphate group, a hydroxy group, a primary to tertiary amino group, a salt of a carboxy group, a salt of a sulfonic acid group, a salt of a phosphonic acid group, a salt of a phosphate group, a salt of a hydroxy group, or a salt of a primary to tertiary amino group. Among these, an allyl group is preferred as the substituent in Ar1 and Ar2.

[0034] Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0035] Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include a monovalent chain hydrocarbon group, a monovalent alicyclic hydrocarbon group, and a monovalent aromatic hydrocarbon group.

[0036] Examples of the chain hydrocarbon group include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and n-pentyl groups; alkenyl groups such as ethenyl, propenyl, butenyl, and pentenyl groups; and alkynyl groups such as ethynyl, propynyl, butynyl, and pentynyl groups.

[0037] Examples of the monovalent alicyclic hydrocarbon group include monocyclic cycloalkyl groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group; polycyclic cycloalkyl groups such as a norbornyl group and an adamantyl group; monocyclic cycloalkenyl groups such as a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, and a cyclohexenyl group; and polycyclic cycloalkenyl groups such as a norbornenyl group.

[0038] Examples of the monovalent aromatic hydrocarbon group include aryl groups such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and an anthryl group; and aralkyl groups such as a benzyl group, a phenethyl group, a phenylpropyl group, and a naphthylmethyl group.

[0039] Examples of the monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms include groups in which some or all of the hydrogen atoms of the monovalent hydrocarbon group having 1 to 20 carbon atoms have been substituted with halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0040] Examples of the alkoxy group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, and an octyloxy group.

[0041] Examples of the alkylthio group having 1 to 20 carbon atoms include a methylthio group, an ethylthio group, an n-propylthio group, an isopropylthio group, a butylthio group, a pentylthio group, a hexylthio group, and an octylthio group.

[0042] The substituent (R) in the secondary amino group (-NHR) and the tertiary amino group (-NR2) is not particularly limited, and examples thereof include monovalent hydrocarbon groups having 1 to 20 carbon atoms. Specific examples of the substituent (R) include the groups exemplified below as substituents in the nitrogen-containing heteroaromatic ring.

[0043] The cations constituting the cationic moieties in the salts of the carboxyl group, the salts of the sulfonic acid group, the salts of the phosphonic acid group, the salts of the phosphoric acid group, and the salts of the hydroxyl group are not particularly limited, and include Na + Examples of known cations include: The anion constituting the anion moiety in the salt of the amino group is not particularly limited, and may be Cl - Examples of known anions include:

[0044] In view of the fact that a cured product with a high crosslink density can be easily obtained, Ar1 and Ar2 may each independently be an aromatic hydrocarbon group having an allyl group.

[0045] The divalent organic group for L is preferably a divalent organic group having 1 to 20 carbon atoms, and examples thereof include a methylene group, an alkanediyl group having 2 to 20 carbon atoms, a halogenated methylene group, a halogenated alkanediyl group having 2 to 20 carbon atoms, a divalent cardo structure, or a group represented by the following formula (L1):

[0046] [ka]

[0047] In formula (L1), R c is an unsubstituted or substituted divalent alicyclic hydrocarbon group having 5 to 30 ring members.

[0048] Examples of the alkanediyl group having 2 to 20 carbon atoms for L include an ethanediyl group, a propane-1,3-diyl group, a propane-2,2-diyl group, a butane-1,4-diyl group, a butane-2,3-diyl group, a pentane-1,3-diyl group, a 4-methyl-pentane-2,2-diyl group, a nonane-1,9-diyl group, and a decane-1,1-diyl group.

[0049] Examples of the halogenated methylene group for L include groups in which some or all of the hydrogen atoms of a methylene group have been substituted with halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0050] Examples of the halogenated alkanediyl group having 2 to 20 carbon atoms for L include groups in which some or all of the hydrogen atoms of the alkanediyl group having 2 to 20 carbon atoms have been substituted with halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0051] An example of the divalent cardo structure in L is a divalent group derived from fluorene represented by the following formula (L2) (that is, a group obtained by removing two hydrogen atoms from a compound having a fluorene skeleton).

[0052] [ka]

[0053] In formula (L2), R8 and R9 each independently represent a hydrogen atom, a fluorine atom, or a monovalent chain hydrocarbon group having 1 to 20 carbon atoms, and k independently represents an integer of 0 to 4.

[0054] Examples of the divalent cardo structure include structures derived from compounds represented by the following formulas:

[0055] [ka]

[0056] R c Examples of the unsubstituted or substituted divalent alicyclic hydrocarbon group having 5 to 30 ring members represented by the formula (I) include an unsubstituted or substituted monocyclic alicyclic hydrocarbon group having 5 to 15 ring members, an unsubstituted or substituted monocyclic fluorinated alicyclic hydrocarbon group having 5 to 15 ring members, an unsubstituted or substituted polycyclic alicyclic hydrocarbon group having 7 to 30 ring members, and an unsubstituted or substituted polycyclic fluorinated alicyclic hydrocarbon group having 7 to 30 ring members.

[0057] Examples of the unsubstituted or substituted monocyclic alicyclic hydrocarbon group having 5 to 15 ring members include a cyclopentane-1,1-diyl group, a cyclohexane-1,1-diyl group, a 3,3,5-trimethylcyclohexane-1,1-diyl group, a cyclopentene-3,3-diyl group, a cyclohexene-3,3-diyl group, a cyclooctane-1,1-diyl group, a cyclodecane-1,1-diyl group, a cyclododecane-1,1-diyl group, and groups in which some or all of the hydrogen atoms of these groups have been substituted with a monovalent chain hydrocarbon group having 1 to 20 carbon atoms.

[0058] Examples of the unsubstituted or substituted monocyclic fluorinated alicyclic hydrocarbon group having 5 to 15 ring members include groups in which some or all of the hydrogen atoms of the groups exemplified as the monocyclic alicyclic hydrocarbon group having 5 to 15 ring members have been substituted with fluorine atoms.

[0059] Examples of the unsubstituted or substituted polycyclic alicyclic hydrocarbon group having 7 to 30 ring members include norbornane, norbornene, adamantane, tricyclo[5.2.1.0 2,6 ] Decane, Tricyclo[5.2.1.0 2,6 ]heptane, pinane, camphane, decalin, nortricyclane, perhydroanthracene, perhydroazulene, cyclopentanohydrophenanthrene, bicyclo[2.2.2]-2-octene, and other polycyclic alicyclic hydrocarbons by removing two hydrogen atoms bonded to one carbon atom; and groups in which some or all of the hydrogen atoms of these groups have been substituted with monovalent chain hydrocarbon groups having 1 to 20 carbon atoms.

[0060] Examples of the unsubstituted or substituted fluorinated polycyclic hydrocarbon group having 7 to 30 ring members include groups in which some or all of the hydrogen atoms of the groups exemplified as the polycyclic alicyclic hydrocarbon group having 7 to 30 ring members have been substituted with fluorine atoms.

[0061] -N(R 8 )-R in 8 represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, and examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms and the monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms include the monovalent hydrocarbon groups having 1 to 20 carbon atoms and the monovalent halogenated hydrocarbon groups having 1 to 20 carbon atoms exemplified above for Ar1, respectively.

[0062] From the viewpoint of structural stability of the polymer (A), L is preferably a single bond, -O-, -S-, -C(O)-, -S(O)-, -S(O)2-, -C(O)-NH-, -C(O)-O-, a methylene group, an alkanediyl group having 2 to 5 carbon atoms, a halogenated methylene group, a halogenated alkanediyl group having 2 to 10 carbon atoms, or a divalent cardo structure. From the same viewpoint, y is preferably an integer of 0 to 4, and more preferably an integer of 0 to 3.

[0063] R 6 and R 7 Examples of the alkanediyl group having 2 to 4 carbon atoms in R include an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, and a sec-butylene group. 6 and R 7 are each independently preferably a single bond, a methylene group, or an ethylene group, from the viewpoint of enabling the synthesis of polymer (A) with good polymerization reactivity.

[0064] R 1Examples of monomers that can be used as raw materials for the portion containing the formula (I) include dihydroxyphenyl compounds such as hydroquinone, resorcinol, catechol, and phenylhydroquinone; 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, bis(4-hydroxyphenyl)diphenylmethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-allylphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-phenylphenyl)propane, 4,4'-(1,3-dimethylbutylidene)bisphenol, and 1,1-bis(4-hydroxyphenyl) )-nonane, bis(4-hydroxyphenyl)sulfone, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(3-methyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,4-bis[2-(4-hydroxyphenyl)-2-propyl]benzene, 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene, 4,4'-cyclododecylidenebisphenol, 4,4'-decylidenebisphenol, and other bisphenol compounds; and diol compounds such as Priplast 1901, 1838, 3186, 3192, 3197, and 3199 (manufactured by Croda Japan Co., Ltd.). These monomers may be used alone or in combination of two or more.

[0065] R 2 represents a divalent unsubstituted or substituted nitrogen-containing heteroaromatic ring. Specific examples of the nitrogen-containing heteroaromatic ring include a pyrrole ring, a pyridine ring, a pyrimidine ring, a pyrazine ring, a pyridazine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a quinoxaline ring, a phthalazine ring, a quinazoline ring, a naphthyridine ring, a carbazole ring, an acridine ring, and a phenazine ring.

[0066] As the nitrogen-containing heteroaromatic ring, a pyrimidine ring is preferred from the viewpoints that the polymer (A) can be synthesized with good polymerization reactivity and that the polymer (A) having excellent solubility in various organic solvents can be easily obtained.

[0067] The positions of the two bonds bonded to the nitrogen-containing heteroaromatic ring (the bonds bonded to X) are not particularly limited, but meta positions are preferred from the viewpoint of synthesizing the polymer (A) with good polymerization reactivity.

[0068] Examples of the substituent in the nitrogen-containing heteroaromatic ring include a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a group in which a portion of these hydrocarbon groups or halogenated hydrocarbon groups is substituted with at least one atom selected from oxygen atoms and sulfur atoms, a nitro group, a cyano group, an amino group, and a salt of an amino group.

[0069] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0070] Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include a monovalent chain hydrocarbon group, a monovalent alicyclic hydrocarbon group, and a monovalent aromatic hydrocarbon group.

[0071] Examples of the chain hydrocarbon group include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and n-pentyl groups; alkenyl groups such as ethenyl, propenyl, butenyl, and pentenyl groups; and alkynyl groups such as ethynyl, propynyl, butynyl, and pentynyl groups.

[0072] Examples of the monovalent alicyclic hydrocarbon group include monocyclic cycloalkyl groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group; polycyclic cycloalkyl groups such as a norbornyl group and an adamantyl group; monocyclic cycloalkenyl groups such as a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, and a cyclohexenyl group; and polycyclic cycloalkenyl groups such as a norbornenyl group.

[0073] Examples of the monovalent aromatic hydrocarbon group include aryl groups such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and an anthryl group; and aralkyl groups such as a benzyl group, a phenethyl group, a phenylpropyl group, and a naphthylmethyl group.

[0074] Examples of the monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms include groups in which some or all of the hydrogen atoms of the monovalent hydrocarbon group having 1 to 20 carbon atoms have been substituted with halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0075] Specific examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms or the monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms partially substituted with at least one atom selected from oxygen atoms and sulfur atoms include groups in which the hydrocarbon group or halogenated hydrocarbon group is partially substituted with -O-, -S-, an ester group, or a sulfonyl group.

[0076] The amino group is not particularly limited, and may be a primary amino group (-NH2), a secondary amino group (-NHR), or a tertiary amino group (-NR2). The substituent (R) in the secondary amino group and tertiary amino group is not particularly limited, and examples thereof include the above-mentioned monovalent hydrocarbon groups having 1 to 20 carbon atoms. The anion constituting the anion moiety in the salt of the amino group is not particularly limited, and may be Cl - Examples of known anions include:

[0077] As the substituent on the nitrogen-containing heteroaromatic ring, from the viewpoints of enabling the synthesis of polymer (A) with good polymerization reactivity and improving the solubility of the monomers serving as raw materials for polymer (A), a halogen atom, a monovalent hydrocarbon group having 1 to 6 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 6 carbon atoms, a nitro group, a cyano group, an amino group, or a salt of an amino group is preferred, and a fluorine atom, a chlorine atom, a methyl group, a nitro group, a cyano group, a tert-butyl group, a phenyl group, or a primary amino group is more preferred.

[0078] R 2Examples of the monomers that can be used as raw materials for the portion containing -phenyl-4,6-dichloropyrimidine, 2-methylthio-4,6-dichloropyrimidine, 2-methylsulfonyl-4,6-dichloropyrimidine, 5-methyl-4,6-dichloropyrimidine, 2-amino-4,6-dichloropyrimidine, 5-amino-4,6-dichloropyrimidine, 2,5-diamino-4,6-dichloropyrimidine, 4-amino-2,6-dichloropyrimidine, 5-methoxy-4,6- pyrimidine compounds such as dichloropyrimidine, 5-methoxy-2,4-dichloropyrimidine, 2-methyl-4,6-dichloropyrimidine, 6-methyl-2,4-dichloropyrimidine, 5-methyl-2,4-dichloropyrimidine, 5-nitro-2,4-dichloropyrimidine, 4-amino-2-chloro-5-fluoropyrimidine, 2-methyl-5-amino-4,6-dichloropyrimidine, and 5-bromo-4-chloro-2-methylthiopyrimidine; pyridazine compounds such as 3,6-dichloropyridazine, 3,5-dichloropyridazine, and 4-methyl-3,6-dichloropyridazine; and pyrazine compounds such as 2,3-dichloropyrazine, 2,6-dichloropyrazine, 2,5-dibromopyrazine, 2,6-dibromopyrazine, 2-amino-3,5-dibromopyrazine, and 5,6-dicyano-2,3-dichloropyrazine. These monomers may be used alone or in combination of two or more.

[0079] In the formula (1), each X is independently -O-, -S-, or -N(R 3 )-. When X is -O-, it is preferable in terms of flexibility, solubility, and heat resistance. 3 )- is preferable in terms of adhesion and the like.

[0080] R 3is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, or a group in which a portion of such a hydrocarbon group or halogenated hydrocarbon group is substituted with at least one atom selected from an oxygen atom and a sulfur atom. R 3 In the above, examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms and the monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms include the monovalent hydrocarbon group having 1 to 20 carbon atoms and the monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms exemplified for Ar1. 3 Specific examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms or the monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms partially substituted with at least one atom selected from oxygen atoms and sulfur atoms include groups in which the hydrocarbon group or halogenated hydrocarbon group is partially or entirely substituted with an ester group or a sulfonyl group.

[0081] R 3 As the group, a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms is preferred from the viewpoint of enabling the synthesis of polymer (A) with good polymerization reactivity. In addition, in formula (1), R 1 Both Xs on both sides are -N(R 3 )-, then two R 3 may be the same or different.

[0082] The polymer (A) may generally have repeating units other than the repeating unit represented by the formula (1) as necessary. Accordingly, the repeating units represented by the formula (1) are bonded to each other, or to the other repeating units or to the terminal group Y represented by the formula (a) described below. When the polymer (A) has a plurality of repeating units represented by formula (1), a plurality of R 1 may be the same or different. This means that R 2 and similarly for other repeating units.

[0083] Examples of the monomer that derives the other repeating units include compounds that derive repeating units containing a carbonate bond, a thiocarbonate bond, or a selenocarbonate bond, such as diphenyl carbonate, diphenyl thiocarbonate, diphenyl selenocarbonate, phosgene, thiophosgene, and selenophosgene; dihydroxy compounds such as benzene dimethanol and cyclohexane dimethanol; phosphine oxide compounds such as bis(fluorophenyl)phenylphosphine oxide, bis(fluorophenyl)naphthylphosphine oxide, and bis(fluorophenyl)anthrylphosphine oxide; and dihalides of dicarboxylic acids such as phthalic acid dichloride, isophthalic acid dichloride, and terephthalic acid dichloride. These monomers may be used alone or in combination of two or more.

[0084] Examples of the repeating unit represented by formula (1) include a repeating unit represented by the following formula (1A) and a repeating unit represented by the following formula (1B).

[0085] [ka]

[0086] [ka]

[0087] In formulas (1A) and (1B), -N(R')-R 3 -N(R')- is a structure derived from unsubstituted or substituted dimer diamine, and R', R 1 and R 2 are each independently a hydrogen atom, a halogen atom, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted heterocyclic aliphatic group having 3 to 20 carbon atoms, or an unsubstituted or substituted heterocyclic aromatic group having 3 to 20 carbon atoms, and R 4represents a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms, a divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms, a divalent chain hydrocarbon group having 1 to 20 carbon atoms, -(R 41 -O) m -, a divalent silicon-containing group, a group consisting of a combination of two or more selected from these groups, a group in which at least a portion of these groups is substituted with at least one atom selected from oxygen atoms, nitrogen atoms and sulfur atoms, or a group in which a portion of these groups is substituted with a substituent, and R 41 are independently an alkanediyl group having 2 to 4 carbon atoms, m is an integer of 1 to 70, and —NR 1 R 2 is R 1 and R 2 and may be a nitrogen-containing heterocyclic group having 5 to 20 ring atoms in which they are bonded to each other, and -N(R')-R 4 -R' and R 4 and may be bonded to each other to form a divalent monocyclic nitrogen-containing heterocyclic group having 5 to 20 ring atoms, -N(R')-R 4 -N(R')- may be a divalent monocyclic nitrogen-containing heterocyclic group having 5 to 20 ring atoms in which two R's are bonded to each other.

[0088] When the polymer (A) has a repeating unit represented by the above formula (1A) and a repeating unit represented by the above formula (1B), the polymer (A) preferably has, at its terminal, a (meth)acryloyloxy group and a group represented by CH═CR-* (wherein R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and * represents a bonding site to another structure).

[0089] The polymer (A) is preferably a polymer having a group represented by the following formula (a) at its terminal: That is, the terminal group Y (terminal structure) of the polymer (A) is represented by the following formula (a).

[0090] [ka]

[0091] In formula (a), Y represents a group containing an ethylenically unsaturated double bond having 3 to 50 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an unsubstituted or substituted aliphatic hydrocarbon group having 6 to 50 carbon atoms, or an unsubstituted nitrogen-containing heteroaromatic ring, and when the aromatic hydrocarbon group or the aliphatic hydrocarbon group has a substituent, the substituent is a group other than a hydroxy group.

[0092] The terminal group Y is bonded to the main chain terminal of the polymer (A), and specifically forms the terminal portion of the polymer (A) represented by the following formula (a1) or (a2). 1 , R 2 and the ends at X (e.g., Ar1, Ar2 and R 2 The substituent in X is -N(R 3 )-R in 3 ) is a group different from the groups constituting the group.

[0093] [ka]

[0094] In the formulae (a1) and (a2), Y has the same meaning as Y in the formula (a). X, R 1 and R 2 respectively represent X and R in the formula (1). 1 and R 2 is synonymous with. X' is a single bond, -O-, -S- or -N(R 3 )-. R 3 is R in the formula (1) 3 is synonymous with.

[0095] In order to improve the dielectric properties, the terminal group Y is preferably an aromatic or aliphatic hydrocarbon group or a nitrogen-containing heteroaromatic ring with low polarization, and when it further contains an ethylenically unsaturated double bond, the crosslink density can be improved, and therefore heat resistance and curability can be expected.

[0096] The group containing an ethylenically unsaturated double bond having 3 to 50 carbon atoms is preferably at least one group selected from the group consisting of a (meth)acryloyloxy group and a group containing a group represented by CH═CR-* (wherein R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and * represents a bonding site to another structure). Specific examples of the group containing an ethylenically unsaturated double bond include aromatic ring-containing groups such as a 3-isopropenylphenyl group, a 4-isopropenylphenyl group, a 2-allylphenyl group, a 2-methoxy-4-allylphenyl group, a 4-(1-propenyl)-2-methoxyphenyl group, a 4-vinylbenzyl group, a 3-vinylbenzyl group, and a 2-vinylbenzyl group, an allyl group, an acryl group, a methacryl group, and a methallyl group.

[0097] Examples of aromatic hydrocarbon groups having 6 to 50 carbon atoms include aryl groups such as phenyl, biphenyl, tolyl, xylyl, naphthyl, and anthryl; and aralkyl groups such as benzyl, phenethyl, phenylpropyl, and naphthylmethyl.

[0098] Examples of the aliphatic hydrocarbon group having 6 to 50 carbon atoms include monocyclic cycloalkyl groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group; polycyclic cycloalkyl groups such as a norbornyl group and an adamantyl group; monocyclic cycloalkenyl groups such as a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, and a cyclohexenyl group; and polycyclic cycloalkenyl groups such as a norbornenyl group.

[0099] The unsubstituted nitrogen-containing heteroaromatic ring includes the R 2 Examples of the rings include the same rings as those exemplified in

[0100] The substituents in the unsubstituted or substituted aromatic hydrocarbon group having 6 to 50 carbon atoms, the unsubstituted or substituted aliphatic hydrocarbon group having 6 to 50 carbon atoms, and the unsubstituted nitrogen-containing heteroaromatic ring are groups other than a hydroxy group, and specific examples include the same groups as those exemplified as the substituents in Ar1. The substituent is not particularly limited, and examples thereof include an allyl group, a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, a nitro group, a cyano group, a carboxy group, a sulfonic acid group, a phosphonic acid group, a phosphate group, a primary to tertiary amino group, a salt of a carboxy group, a salt of a sulfonic acid group, a salt of a phosphonic acid group, a salt of a phosphate group, and a salt of a primary to tertiary amino group. Among these, an allyl group is preferred as the substituent for Ar1.

[0101] R in the formula (1) 1 or R 2 In addition to the monomer that gives the above, at least one monomer for forming the terminal group Y selected from the group consisting of a monohydric phenol, a monovalent amine, a monovalent thiol, a monovalent aromatic, a monovalent aliphatic halide, a monovalent acid halide, and a monovalent acid anhydride is used as a raw material and reacted to obtain a polymer (A) whose ends are capped with the terminal group Y. When synthesizing a polymer (A) in which the terminal group Y contains a double bond, for example, R 1 The monomers that are the raw materials for the part containing R 2 During polymerization with the monomer that is the raw material for the portion containing R, the double bonds in the monomer that forms the terminal group Y react with each other to prevent gelation. 1 The monomers that are the raw materials for the part containing R 2 After polymerization with the monomer that is the raw material for the portion containing the group Y, a monomer for forming the terminal group Y may be added and reacted.

[0102] Examples of the monomer for forming the terminal group Y include monohydric phenol compounds such as t-butylphenol, nonylphenol, 4-isopropenylphenol, 4-vinylphenol, 2-allylphenol, isoeugenol, tocotrienol, α-tocophenol, 4-hydroxyphenylmaleimide, and 2-phenylphenol; monovalent amine compounds such as 4-hexylaniline and diallylamine; monovalent thiol compounds such as 1-octanethiol; monovalent aliphatic halides such as allyl chloride, 4-(chloromethyl)styrene, and 3-(chloromethyl)styrene; monovalent acid halides such as acrylic chloride, methacrylic chloride, crotonoyl chloride, and cinnamoyl chloride; and monovalent acid anhydrides such as acrylic anhydride, crotonic anhydride, and methacrylic anhydride. These monomers may be used alone or in combination of two or more.

[0103] The content of the repeating unit represented by the formula (1) in the polymer (A) is preferably 30 mol% or more, more preferably 50 mol% or more, even more preferably 60 mol% or more, and is preferably 99.5 mol% or less, more preferably 98 mol% or less, even more preferably 95 mol% or less.

[0104] <Sequence of each repeating unit> Examples of the polymer (A) having the repeating unit represented by formula (1) and the terminal group Y represented by formula (a) include polymers having a combination of these repeating units in the main chain, and specific examples include polymers represented by the following formulas (3) or (4). Here, the "main chain" refers to the relatively longest connecting chain in the polymer.

[0105] [ka]

[0106] In the above formula, R 1 , R 2 , X, Y and X′ are R in the formulas (1), (a), (a1) and (a2). 1 , R 2, X, Y and X′ are synonymous with each other. n is an integer of 0 to 100, and more preferably 2 to 30. In the above formula, a plurality of R 1 , R 2 , X, Y and X' may be the same or different.

[0107] Examples of the polymer (A) include the following exemplary compounds, but the present invention is not limited to these.

[0108] [ka]

[0109] [ka]

[0110] [ka]

[0111] [ka]

[0112] [ka]

[0113] <Method for synthesizing polymer (A)> The method for synthesizing the polymer (A) is not particularly limited, and known methods can be used. 1 and a monomer serving as a raw material for the portion containing R 2 The monomer for deriving the other repeating unit and the monomer for forming the terminal group Y can be synthesized by heating them together in an organic solvent with an alkali metal or an alkali metal compound. 1and a monomer serving as a raw material for the portion containing R 2 After polymerizing the monomers that are the raw materials for the portion containing the monomer, the mixture may be heated and mixed to cause a reaction.

[0114] When a compound having a hydroxy group, such as a phenol compound, is used as a raw material in the synthesis of polymer (A), the alkali metal and alkali metal compound react with the compound having a hydroxy group to form an alkali metal salt. Examples of such alkali metals and alkali metal compounds include: Alkali metals such as lithium, sodium, and potassium; Alkali metal hydrides such as lithium hydride, sodium hydride, and potassium hydride; Alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; Alkali metal carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate; Examples include alkali metal hydrogen carbonates such as lithium hydrogen carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate. Of these, alkali metal carbonates are preferred, with potassium carbonate being more preferred.

[0115] When a compound having a hydroxy group is used in synthesizing the polymer (A), the amount of alkali metal and alkali metal compound used is such that the lower limit of the ratio of the number of moles of alkali metal atoms to the number of moles of hydroxy groups in all compounds used in synthesizing the polymer (A) is preferably 1, more preferably 1.1, and even more preferably 1.2, and the upper limit of said ratio is preferably 3, more preferably 2, and even more preferably 1.8.

[0116] Examples of the organic solvent include ether solvents such as tetrahydrofuran (THF), dioxane, cyclopentyl methyl ether, anisole, phenetole, diphenyl ether, dialkoxybenzene, and trialkoxybenzene; Nitrogen-containing solvents such as N,N-dimethylacetamide (DMAc), N,N-dimethylformamide, N-methyl-2-pyrrolidone, and 1,3-dimethyl-2-imidazolidinone; ester solvents such as gamma-butyrolactone; sulfur-containing solvents such as sulfolane, dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, diethyl sulfone, diisopropyl sulfone, and diphenyl sulfone; ketone solvents such as benzophenone, 2-heptanone, cyclohexanone, and methyl ethyl ketone; Halogenated solvents such as methylene chloride, chloroform, and chlorobenzene; Examples of the solvent include aromatic hydrocarbon solvents such as benzene, toluene, and xylene. Of these organic solvents, 2-heptanone, cyclohexanone, N-methyl-2-pyrrolidone, toluene, and xylene are preferred, and N-methyl-2-pyrrolidone, 2-heptanone, and cyclohexanone are more preferred.

[0117] The lower limit of the reaction temperature during the synthesis is preferably 50°C, more preferably 80°C, and the upper limit is preferably 300°C, more preferably 200°C. The lower limit of the reaction time in the synthesis is preferably 1 hour, more preferably 2 hours, and even more preferably 3 hours, and the upper limit is preferably 100 hours, more preferably 50 hours, and even more preferably 24 hours.

[0118] For the purpose of suppressing gelation of the polymerization solution, the lower limit of the reaction temperature when the monomer for forming the terminal group Y is added after polymerization is preferably 0°C, more preferably 10°C, and the upper limit is preferably 130°C, more preferably 110°C. The lower limit of the reaction time when the monomer for forming the terminal group Y is added after polymerization and reacted is preferably 1 hour, more preferably 2 hours, and even more preferably 3 hours, and the upper limit is preferably 48 hours, more preferably 24 hours, and even more preferably 10 hours.

[0119] [Physical properties of polymer (A)] The lower limit of the weight average molecular weight (Mw) of the polymer (A) in terms of polystyrene is preferably 1,000, more preferably 2,000, even more preferably 3,000, and particularly preferably 5,000, and the upper limit is preferably 500,000, more preferably 100,000, even more preferably 50,000, particularly preferably 30,000, and most preferably 15,000. The polymer (A) having an Mw within the above range is preferred because it has a good balance of excellent adhesion, heat resistance, impregnation into glass cloth, moldability such as resin flow, and the like. In the present invention, Mw is a value measured by gel permeation chromatography (GPC) under the conditions described in the following examples.

[0120] The dielectric loss tangent (tanδ) of the polymer (A) is preferably less than 0.0030, more preferably 0.0020 or less, and even more preferably 0.0012 or less, from the viewpoint of being able to reduce transmission loss when a composition containing the polymer (A) is prepared, and the lower limit is not particularly limited, but is preferably 0.0005 or more. Specifically, the dielectric loss tangent can be measured by the method described in the examples below.

[0121] The content of polymer (A) is, for example, preferably 0.05% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, relative to 100% by mass of the total solid content in the resin composition, and is preferably 99.95% by mass or less, more preferably 90% by mass or less, even more preferably 80% by mass or less. The content of the polymer (A) within the above range is preferable from the viewpoint of further improving the adhesiveness, heat resistance, curability, and electrical properties of the cured product obtained from the resin composition. The polymer (A) may be used alone or in combination of two or more kinds, and the resin composition may be a mixture of two or more kinds of polymer (A). When two or more types of polymers (A) are used, polymers (A) having different weight average molecular weights (Mw) within the range of the weight average molecular weight (Mw) of the polymer (A) can be mixed depending on the desired physical properties, for example.

[0122] <<Compound (B)>> The resin composition contains compound (B). Compound (B) is a hindered amine compound (B1) having no electron-withdrawing group other than a nitroxy radical group, and a hindered amine compound (B2) having an electron-withdrawing group other than a nitroxy radical group.

[0123] <<Compound (B1)>> The hindered amine compound (B1) (hereinafter also simply referred to as "compound (B1)") does not have any electron-withdrawing group other than the nitroxy radical group. The compound (B1) is not particularly limited as long as it has a nitroxy radical group in one molecule and does not have any electron-withdrawing group other than the nitroxy radical group. Here, the hindered amine compound refers to an amine compound having bulky structures on both sides of an amino group. Examples of amine compounds having bulky structures include amine compounds having a structure with tertiary alkyl groups on both sides of an amino group and amine compounds having a structure containing a bridged ring having seven or more ring members. Examples of bridged rings having seven or more ring members include bridged ring hydrocarbon structures such as norbornane, adamantane, and norbornene; and polycyclic aliphatic heterocyclic structures such as diazabicyclooctane.

[0124] Examples of compound (B1) include 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), 2,2,6,6-tetraethyl-1-piperidinyloxy radical, 2,2,5,5-tetramethyl-1-pyrrolidinyloxy radical, 1,1,3,3-tetramethyl-2-isoindolinyloxy radical, di-tert-butyl-nitroxide (DBN), tetramethyl-isoindoline-1-oxyl, 9-azanoradamantane-N-oxyl (nor-AZADO), and 9-azabicyclo[3.3.1]nonane-N-oxyl (ABNO).

[0125] Among these, compound (B1) is preferably a compound having an adamantane structure or a piperidine structure and a nitroxy radical group, and more preferably a compound represented by the following formula (B1-1) (2,2,6,6-tetramethylpiperidine-1-oxyl).

[0126] [ka]

[0127] The content of the compound (B1) is 0.1 parts by mass or more and 10 parts by mass or less, preferably 0.1 parts by mass or more and 5 parts by mass or less, and more preferably 0.1 parts by mass or more and 3 parts by mass or less, relative to 100 parts by mass of the polymer (A). The compound (B1) may be contained in the resin composition either as a single type or as a combination of two or more types.

[0128] <<Compound (B2)>> The hindered amine compound (B2) (hereinafter also simply referred to as "compound (B2)") has an electron-withdrawing group other than a nitroxy radical group. Compound (B2) is not particularly limited as long as it is a compound having an electron-withdrawing group other than a nitroxy radical group, and may be a compound having both a nitroxy radical group and an electron-withdrawing group other than a nitroxy radical group in one molecule. In this specification, the electron-withdrawing group refers to a substituent having a positive Hammett σp value. For the Hammett σp value, see Hansch, C.; Leo, A.; Taft, R. W. Chem. Rev. 1991, 91, 165-195. Examples of the electron-withdrawing group include a hydroxy group, a carboxy group, an alkoxy group (here, the alkoxy group includes an alkoxy group having 1 to 8 carbon atoms), a nitro group, a nitroso group, a cyano group, a halogen atom such as a chlorine atom, a bromine atom, or a fluorine atom; and a haloalkyl group such as a perfluoroalkyl group or a perchloroalkyl group (here, the alkyl group includes a linear, branched, or cyclic, saturated or unsaturated alkyl group having 1 to 8 carbon atoms).

[0129] The compound (B2) is preferably a compound represented by the following formula (B2-1).

[0130] [ka]

[0131] In formula (B2-1), R B21 represents an electron-withdrawing group other than a nitroxy radical group, and n B21 represents an integer from 1 to 6.

[0132] R B21 Examples of the nitroxy radical group include electron-withdrawing groups other than the above-mentioned nitroxy radical group. B21 is preferably a hydroxy group, a carboxy group, an alkoxy group or amino group having 1 to 8 carbon atoms, or a cyano group, and more preferably a hydroxy group, a carboxy group, or an alkoxy group having 1 to 4 carbon atoms.

[0133] n B21 is preferably an integer of 1 to 4, more preferably an integer of 1 to 3, even more preferably 1 or 2, and particularly preferably 1.

[0134] Examples of compound (B2) include 4-carboxy-2,2,6,6-tetramethylpiperidine-1-oxyl (4-carboxy-TEMPO), 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl (4-oxo-TEMPO), 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl (4-methoxy-TEMPO), 4-cyano-2,2,6,6-tetramethylpiperidine-1-oxyl (4-cyano-TEMPO), 4-oxybenzoyl-2,2,6,6-tetramethylpiperidine-1-oxyl (4-oxybenzoyl-TEMPO), and 2,2,6,6-tetramethyl-4-oxo-1-piperidinyloxy radical (4-oxo-TEMPO free radical). Examples of the compound (B2) include the following exemplary compounds, but the present invention is not limited to these compounds.

[0135] [ka]

[0136] The content of the compound (B2) is preferably 0.0005 parts by mass or more and 1 part by mass or less, more preferably 0.001 parts by mass or more and 0.5 parts by mass or less, and even more preferably 0.005 parts by mass or more and 0.3 parts by mass or less, relative to 100 parts by mass of the polymer (A). The compound (B2) may be contained in the resin composition either as a single type or as a combination of two or more types.

[0137] <<Solvent (C)>> The resin composition contains a solvent (C). The solvent (C) is not particularly limited, and examples thereof include amide solvents such as N,N-dimethylformamide, ester solvents such as γ-butyrolactone and butyl acetate, ketone solvents such as cyclopentanone, cyclohexanone, methyl ethyl ketone and 2-heptanone, ether solvents such as 1,2-methoxyethane, anisole and tetrahydrofuran, polyfunctional solvents such as 1-methoxy-2-propanol and propylene glycol methyl ether acetate, sulfone solvents such as dimethyl sulfoxide, methylene chloride, benzene, toluene, xylene, and trialkoxybenzene (number of carbon atoms in the alkoxy group: 1 to 4).

[0138] When the resin composition contains a solvent, the content of the solvent in the resin composition is not particularly limited, but is, for example, preferably 0 parts by mass or more and 2000 parts by mass or less, more preferably 0 parts by mass or more and 1000 parts by mass or less, per 100 parts by mass of the total solid content of the polymer (A). When the polymer (A) has high solubility in the solvent, the content of the solvent in the resin composition may be 50 parts by mass or more and 200 parts by mass or less.

[0139] [Curable compound (D)] The resin composition may contain a curable compound (D) other than the polymer (A). The curable compound (D) (hereinafter also referred to as "compound (D)") is a compound other than the polymer (A). Examples of such compound (D) include vinyl compounds, maleimide compounds, allyl compounds, acrylic compounds, methacrylic compounds, acrylamide compounds, phenol compounds, thiol compounds, oxazine compounds, cyanate compounds, epoxy compounds, oxetane compounds, methylol compounds, benzocyclobutene compounds, propargyl compounds, and silane compounds. Among these, at least one of vinyl compounds, maleimide compounds, and allyl compounds is particularly preferred in terms of compatibility with the polymer (A), reactivity, etc. The compound (D) may be used alone or in combination of two or more.

[0140] Examples of the vinyl compound include polyfunctional aromatic vinyl compounds such as divinylbenzene and N-(4-vinylphenyl)maleimide, and styrene-based thermoplastic elastomers such as styrene-butadiene-styrene copolymer (SBS), hydrogenated styrene-butadiene-styrene copolymer (SEBS), styrene-isoprene-styrene copolymer (SIS), hydrogenated styrene-isoprene-styrene copolymer, styrene-butadiene elastomer (SBR), tert-butylstyrene, and 2-vinyl-4,6-diamino-1,3,5-triazine. Further examples of the vinyl compound include TA100 (manufactured by Mitsubishi Gas Chemical Company, Inc.) and ULL-950S (manufactured by LONZA). Examples of the maleimide compound include aromatic compounds having two or more maleimide groups, and polymers whose ends are modified with maleimide groups. Examples of the allyl compound include compounds represented by the following formulas (b-3-1) to (b-3-6).

[0141] [ka]

[0142] The content of compound (D) in the resin composition is, for example, preferably 0.05% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, and is preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 50% by mass or less, when the total solid content in the resin composition is 100% by mass. The content of the compound (D) within the above range is preferable from the viewpoint of further improving the strength and heat resistance of the cured product obtained from the resin composition.

[0143] [Polymerization initiator (E)] The resin composition preferably further contains a polymerization initiator (E). Examples of the polymerization initiator (E) include thermal or photoradical polymerization initiators, cationic curing agents, and anionic curing agents. Among these, the polymerization initiator (E) is preferably a thermal radical polymerization initiator.

[0144] Examples of the thermal radical polymerization initiator include organic peroxides such as dicumyl peroxide, 1,1-di(t-butylperoxy)cyclohexane, di(t-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, and benzoyl peroxide; and azo compounds such as azobisbutyronitrile, 1,1'-azobis(1-acetoxy-1-phenylethane), 2,2'-azobis(2,4-dimethylvaleronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), dimethyl-2,2'-azobis(isobutyrate), and 2,2'-azobis(2-methylbutyronitrile).

[0145] When the resin composition contains a polymerization initiator (E), the content of the polymerization initiator (E) is preferably within a range in which the resin composition is well cured to obtain a cured product. Specifically, the content of the polymerization initiator (E) is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and preferably 20 parts by mass or less, more preferably 10 parts by mass or less, relative to 100 parts by mass of the total solid content of the compound (A) and the polymer (B). The polymerization initiator (E) may be used alone or in combination of two or more kinds.

[0146] Filler The resin composition preferably further contains a filler (F). The filler (F) may be an organic filler or an inorganic filler, such as silicas such as natural silica, fused silica, and amorphous silica, white carbon, titanium white, aerosil, alumina, talc, natural mica, synthetic mica, clay, barium sulfate, E-glass, A-glass, C-glass, L-glass, D-glass, S-glass, and M-glass G20.

[0147] When the resin composition contains a filler (F), the content of the filler (F) is, for example, preferably 0.1 parts by mass or more and 300 parts by mass or less relative to 100 parts by mass of the total solid content of the compound (A) and the polymer (B). The filler (F) may be in a state of being dispersed in a solvent by the polymer (B). The filler (F) may be used alone or in combination of two or more kinds.

[0148] <<Other Ingredients (G)>> The resin composition may further contain components other than the polymer (A), the compound (B), the solvent (C), the curable compound (D), the polymerization initiator (E), and the filler (F) (hereinafter, also simply referred to as "other components (G)"), as long as the effects of the present invention are not impaired. Examples of other components (G) include polymers other than the polymer (A), polymerization inhibitors other than the compound (B), antioxidants, adhesion aids, lubricants, flame retardants, antibacterial agents, colorants, release agents, and foaming agents. These other components may be used singly or in combination of two or more. The content of the other component (G) is preferably 5 parts by mass or less, and more preferably 1 part by mass or less, based on 100 parts by mass of the polymer (A). The other component (G) may be used alone or in combination of two or more.

[0149] [Method for preparing resin composition] The resin composition can be prepared, for example, by uniformly mixing the polymer (A), the compound (B), and the solvent (C), and, if necessary, the curable compound (D), the polymerization initiator (E), the filler (F), and other components (G). In this case, the order of mixing, mixing conditions, etc. are not particularly limited, and a conventionally known mixer may be used for mixing.

[0150] [Cured product] A cured product according to one embodiment of the present invention (hereinafter also referred to as "main cured product") is a cured product of the above-mentioned resin composition, and is obtained by curing the resin composition. The cured product may be, for example, a partially cured product of a resin composition obtained by drying the solvent from the resin composition.

[0151] The method for curing the resin composition is not particularly limited, but typically includes a method of thermal curing by heating or a method of photocuring by irradiating light. These methods can also be used in combination. In the case of thermal curing, the heating temperature is preferably 50° C. or higher, more preferably 100° C. or higher, even more preferably 120° C. or higher, and preferably 250° C. or lower, more preferably 220° C. or lower. The heating time is preferably 0.1 hours or longer, more preferably 0.5 hours or longer, and preferably 36 hours or shorter, more preferably 5 hours or shorter. In the case of photocuring, examples of the light to be irradiated include visible light, ultraviolet light, near infrared light, and far infrared light.

[0152] The lower limit of the Tg of the present cured product is preferably 100°C, more preferably 110°C, and the upper limit is, for example, 300°C. When the Tg is within the above range, melt molding can be carried out more easily, and a cured product having excellent heat resistance can be easily obtained. Tg was measured by preparing a test piece (width: 3 mm x length: 1 cm) and using a dynamic viscoelasticity measuring device (Seiko Instruments Inc., model number "EXSTAR4000"), measuring from 50°C to 300°C at a heating rate of 10°C / min and 1 Hz under nitrogen, and then measuring again at a heating rate of 10°C / min and 1 Hz up to 300°C, and the tan δ at this time was taken as the glass transition temperature (Tg). When two or more tan δ values ​​existed, the lowest value was taken as Tg.

[0153] The dielectric loss tangent (tan δ) of the cured product is preferably 0.0025 or less, more preferably 0.0018 or less, and even more preferably 0.0015 or less, from the viewpoint of reducing transmission loss, and although there is no particular lower limit, it is preferably 0.0005 or more. Specifically, the dielectric loss tangent can be measured by the method described in the examples below.

[0154] The shape of the cured product is not particularly limited and may be any shape suitable for the application or purpose, for example, a film. For example, the resin composition can be melt-molded or cast to obtain a film-like cured product. The thickness of the film is not particularly limited and may be appropriately selected depending on the desired application, but is, for example, 10 μm or more, preferably 30 μm or more, and for example, 2 mm or less, preferably 1 mm or less.

[0155] [Laminate] A laminate according to one embodiment of the present invention (hereinafter, may be referred to as "the present laminate") includes, for example, a substrate and a cured product layer formed from a resin composition. The present laminate may include two or more substrate layers, two or more cured material layers, or other conventionally known layers other than the substrate and the cured material layer. When the present laminate includes two or more substrate layers, cured material layers, or other layers, these may be the same layer (plate) or different layers (plates).

[0156] The present laminate may be a prepreg obtained by impregnating a substrate such as glass cloth, aramid nonwoven fabric, or polyester nonwoven fabric with the resin composition and curing it.

[0157] From the viewpoint of adhesiveness and practicality, the substrate may be an inorganic substrate, a metal substrate, a resin substrate, etc. The substrate may also be a prepreg. Examples of the inorganic substrate include inorganic substrates containing silicon, silicon carbide, silicon nitride, alumina, glass, gallium nitride, and the like as components. Examples of the metal substrate include metal substrates containing copper, aluminum, gold, silver, nickel, palladium, and the like. Examples of the resin substrate include resin substrates containing liquid crystal polymer, polyimide, polyphenylene sulfide, polyether ether ketone, polyamide (nylon), polyethylene terephthalate, polyethylene naphthalate, cycloolefin polymer, polyolefin, and the like.

[0158] The cured product layer can be formed, for example, by curing using the method described in the section on cured products. The thickness of the cured material layer is not particularly limited, but is, for example, 1 μm to 3 mm.

[0159] <<Application>> The polymer (A), resin composition, cured product, and laminate are suitable for use as structural materials in the transportation industry, such as the aircraft and automobile industries, and as electrical and electronic materials in the electrical and electronics industry. Specifically, they can be used in, for example, encapsulants for electrical and electronic components, interlayer insulating films, and stress-relief primers; laminate applications (e.g., prepregs, copper-clad laminates, (multilayer) printed wiring boards, interlayer adhesives, solder resists, and solder pastes); adhesive applications (e.g., adhesive sheets for forming insulating layers, thermally conductive adhesives, and adhesive sheets); structural adhesives and prepregs used in various structural materials; various coatings; optical component applications (e.g., optical films such as wave plates and retardation plates, various specialty lenses such as conical lenses, spherical lenses, and cylindrical lenses, and lens arrays); and insulating films for printed wiring boards.

[0160] [Electronic Components] An electronic component according to one embodiment of the present invention comprises the present cured product or present laminate. The electronic component may comprise two or more present cured products or two or more present laminates, or may comprise one or more present cured products and one or more present laminates. When two or more present cured products or present laminates are present, they may be the same or different.

[0161] Examples of the electronic components include circuit boards, semiconductor packages, and display substrates. The present cured product (cured film) can be used for these electronic components as prepregs, copper-clad laminates, printed wiring boards, adhesive sheets for forming insulating layers, surface protective films, rewiring layers, or planarizing films. Because the present cured product can maintain its insulating properties even under high temperature and high humidity conditions, the electronic components can protect circuit patterns from external environments such as dust, heat, and humidity, and have excellent insulation reliability between circuit patterns, enabling them to operate stably for many years.

[0162] For example, a rewiring layer can be formed by filling metal between the patterns of the cured product (cured film) by plating or the like, and if necessary, stacking more cured products (cured films) and repeating the metal filling process, thereby producing an electronic component having a substrate and a rewiring layer including metal wiring and an insulating film. [Example]

[0163] The present invention will be explained in more detail below based on examples, but the present invention is not limited to these examples in any way.

[0164] [Synthesis Example 1] 2,2-bis(4-hydroxy-3-methylphenyl)propane (26.43 g), 4,6-dichloro-2-phenylpyrimidine (17.08 g), and potassium carbonate (19.23 g) were weighed into a four-neck separable flask equipped with a stirrer, and N-methyl-2-pyrrolidone (42.50 g) was added. The mixture was reacted at 100°C for 6 hours under a nitrogen atmosphere. After the reaction, the vessel was cooled to 10°C, and m,p-(chloromethyl)styrene (11.53 g) was added dropwise, followed by a reaction at 100°C for 4 hours. The resulting reaction solution was diluted with N-methyl-2-pyrrolidone (55.0 g), and the salt was removed from the diluted solution by filtration. The resulting solution was then poured into methanol (6900 g). The precipitated solid was filtered off, washed with a small amount of methanol, and recovered by filtration again. After that, it was dried under reduced pressure at 60°C for 12 hours using a vacuum dryer to obtain a polymer (A1) represented by the following formula (1).

[0165] [ka]

[0166] [Synthesis Example 2] Polymer (A2) represented by the following formula (2) was obtained by synthesizing the polymer in the same manner as in Synthesis Example 1, except that the raw materials and alkali metal compound used in Synthesis Example 1 were changed to 1,1-bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane (33.85 g), 4,6-dichloro-2-phenylpyrimidine (16.66 g), m,p-chloromethylstyrene (8.680 g), potassium carbonate (18.66 g), and N-methyl-2-pyrrolidone (42.50 g), respectively, and washing with methanol was repeated six times.

[0167] [ka]

[0168] [Synthesis Example 3] 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (62.08 g), 4,6-dichloropyrimidine (30.99 g), isopropenylphenol (2.170 g), and potassium carbonate (38.83 g) were weighed into a four-neck separable flask equipped with a stirrer, and N-methyl-2-pyrrolidone (64.00 g) was added. The mixture was reacted at 130°C for 6 hours under a nitrogen atmosphere. After the reaction was completed, the mixture was diluted with N-methyl-2-pyrrolidone (368.0 g). After filtering to remove salts, the resulting solution was poured into methanol (19.4 kg). The precipitated solid was filtered off, washed with a small amount of methanol, and then filtered again. The solid was then dried under reduced pressure at 120°C for 12 hours using a vacuum dryer to obtain a polymer (A3) having a repeating unit represented by the following formula (3):

[0169] [ka]

[0170] [Synthesis Example 5] Polymer (A4) represented by the following formula (4) was obtained in the same manner as in Synthesis Example 3, except that the raw materials and alkali metal compound used in Synthesis Example 3 were changed to 2,2-bis(4-hydroxy-3-methylphenyl)propane (25.63 g), 4,6-dichloro-2-phenylpyrimidine (29.25 g), 2-allylphenol (8.131 g), and potassium carbonate (24.31 g), respectively.

[0171] [ka]

[0172] [Synthesis Example 6] 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (71.13 g), 4,6-dichloropyrimidine (29.79 g), and potassium carbonate (39.27 g) were weighed into a four-neck separable flask equipped with a stirrer, and N-methyl-2-pyrrolidone (64.00 g) was added. The mixture was reacted at 130°C for 6 hours under a nitrogen atmosphere. After the reaction, the vessel was cooled to 10°C, and methacryloyl chloride (6.094 g) was added dropwise, followed by a reaction at 50°C for 6 hours. The resulting reaction solution was diluted with N-methyl-2-pyrrolidone (368.0 g), and the salt was removed from the diluted solution by filtration. The resulting solution was then poured into methanol (19.40 kg). The precipitated solid was filtered off, washed with a small amount of methanol, and recovered by filtration again. After that, it was dried under reduced pressure at 120°C for 12 hours using a vacuum dryer to obtain a polymer (A5) represented by the following formula (5).

[0173] [ka]

[0174] [Synthesis Example 7] Polymer (A6) represented by the following formula (6) was obtained in the same manner as in Synthesis Example 5, except that the raw materials and alkali metal compound used in Synthesis Example 5 were changed to 2,2-bis(4-hydroxy-3-methylphenyl)propane (25.63 g), 4,6-dichloropyrimidine (16.57 g), potassium carbonate (18.65 g), N-methyl-2-pyrrolidone (64.00 g), and methacryloyl chloride (7.657 g), respectively.

[0175] [ka]

[0176] The following commercially available polymer (A7) was used: Terminally modified polyphenylene ether (product name: Noryl TM SA9000 resin, manufactured by Sabic

[0177] [ka]

[0178] [Synthesis Example 8] Monomer 2,2-bis(4-hydroxy-3-methylphenyl)propane (27.26 g), monomer 4,6-dichloro-2-phenylpyrimidine (19.52 g), 4,4',4''-trihydroxytriphenylmethane (3.27 g), and potassium carbonate (21.93 g) were weighed into a four-neck separable flask equipped with a stirrer, and N-methyl-2-pyrrolidone (42.50 g) was added. The mixture was reacted at 100°C for 6 hours under a nitrogen atmosphere. After the reaction, m,p-chloromethylstyrene (11.53 g) was added dropwise to the vessel cooled to 10°C, and the mixture was reacted at 100°C for 4 hours. The resulting reaction solution was diluted with N-methyl-2-pyrrolidone (55.00 g), and the salt was removed from the diluted solution by filtration. The resulting solution was then poured into methanol (6900 g). The precipitated solid was filtered off, washed with a small amount of methanol, and recovered by filtering again. The solid was then dried under reduced pressure at 60° C. for 12 hours using a vacuum dryer to obtain a polymer (A8).

[0179] [ka]

[0180] [Synthesis Example 9] In a four-necked separable flask equipped with a stirrer, 2-phenylamino-4,6-dichloro-s-triazine (AnDCT) (13.6 g), dimer diamine (Priamine 1075) (30.1 g), acryloyl chloride (0.41 g), and potassium carbonate (7.9 g) were weighed out, and cyclohexanone (60.0 g) and water (25.7 g) were added thereto, and the mixture was reacted for 20 hours at 100 ° C. under a nitrogen atmosphere. After the reaction was completed, the aqueous phase was separated using a separatory funnel, and the organic phase was washed with deionized water until neutral. The solvent was then concentrated to obtain a solution of the following polymer (G2) with a solids content of 30% by mass.

[0181] [ka]

[0182] [Synthesis Example 10] 2-phenylamino-4,6-dichloro-s-triazine (AnDCT) (13.6 g), dimer diamine (Priamine 1075) (30.1 g), m,p-chloromethylstyrene (0.43 g), and potassium carbonate (7.9 g) were weighed into a four-necked separable flask equipped with a stirrer, and cyclohexanone (60.0 g) and water (25.7 g) were added thereto. The mixture was reacted for 20 hours at 100 ° C. under a nitrogen atmosphere. After the reaction was completed, the aqueous phase was separated using a separatory funnel, and the organic phase was washed with deionized water until neutral. The solvent was then concentrated to obtain a solution of the following polymer (A21) with a solids content of 30% by mass.

[0183] [ka]

[0184] [Synthesis Example 11] 2-phenylamino-4,6-dichloro-s-triazine (AnDCT) (13.6 g), dimer diamine (Priamine 1075) (30.1 g), diallylamine (0.44 g), and potassium carbonate (7.9 g) were weighed into a four-neck separable flask equipped with a stirrer, and cyclohexanone (60.0 g) and water (25.7 g) were added thereto, and the mixture was reacted for 20 hours at 100 ° C. under a nitrogen atmosphere. After the reaction was completed, the aqueous phase was separated using a separatory funnel, and the organic phase was washed with deionized water until neutral. The solvent was then concentrated to obtain a solution of the following polymer (A22) with a solids content of 30% by mass.

[0185] [ka]

[0186] [Synthesis Example 12] Trichlorotriazine (11.0 g), dimer diamine (Priamine 1075) (30.1 g), and potassium carbonate (7.9 g) were weighed into a four-neck separable flask equipped with a stirrer. Cyclohexanone (60.0 g) and water (25.7 g) were added, and the mixture was reacted at 60°C for 2 hours under a nitrogen atmosphere. After the reaction was completed, diallylamine (9.0 g) and a 1% by weight cyclohexane solution of 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl (5.2 g) were added, and the mixture was reacted at 100°C for an additional 13 hours. After the reaction was completed, the aqueous phase was separated using a separatory funnel, and the organic phase was washed with deionized water until neutral. The solvent was then concentrated to obtain a solution of the following polymer (A23) with a solids content of 30% by weight.

[0187] [ka]

[0188] [Synthesis Example 13] 2-phenylamino-4,6-dichloro-s-triazine (AnDCT) (13.9 g), dimer diamine (Priamine 1075) (30.2 g), 4-(2-aminoethyl)phenol (0.16 g), and potassium carbonate (8.1 g) were weighed into a four-necked separable flask equipped with a stirrer, and cyclohexanone (60.0 g) and water (25.7 g) were added thereto, and the mixture was reacted for 20 hours at 100 ° C. under a nitrogen atmosphere. After the reaction was completed, the aqueous phase was separated using a separatory funnel, and the organic phase was washed with deionized water until neutral. The solvent was then concentrated to obtain a solution of the following polymer (G1) with a solid content of 30% by mass.

[0189] [ka]

[0190] [Comparative polymer (a1)] 1,1-bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane (25.4 g, 75.0 mmol), 4,6-dichloropyrimidine (11.2 g, 75.0 mmol), and potassium carbonate (14.0 g, 101.3 mmol) were weighed into a four-neck separable flask equipped with a stirrer, and N-methyl-2-pyrrolidone (85 g) was added. The mixture was reacted at 130°C for 6 hours under a nitrogen atmosphere. After the reaction was completed, the mixture was diluted with N-methyl-2-pyrrolidone (300 g). The salt was removed by filtration, and the resulting solution was poured into methanol (6 kg). The precipitated solid was filtered, washed with a small amount of methanol, and recovered by filtration again. The solid was then dried under reduced pressure at 120°C for 12 hours using a vacuum dryer to obtain polymer (a1) having a repeating unit represented by the following formula (8):

[0191] [ka]

[0192] [Examples 1 to 13, Examples 20 to 32, Examples 40 to 42, and Comparative Examples 1 to 4] The components listed in Table 1 were mixed in a mixer rotor to the ratios (parts by mass) listed in the composition blending ratio column in Table 2 or Table 3, and the concentration was adjusted with toluene (C-1) to a solids concentration of 50 mass%, to prepare resin compositions. Details of each component in Table 2 or Table 3 are shown in Table 1. Note that "-" in Table 2 and Table 3 means that the corresponding component is not included.

[0193] [Table 1]

[0194] [Table 2]

[0195] [Table 3]

[0196] <Preparation of cured film> The resin compositions obtained in the above Examples and Comparative Examples were applied to copper foil (model number: CF-T49A-DS-HD2, manufactured by Fukuda Metals Co., Ltd.) using a Baker-type applicator (gap: 125 μm), then dried at 100°C for 5 minutes and then at 140°C for 5 minutes, and then baked under nitrogen at 200°C for 2 hours. The resulting cured film with copper foil was immersed in a 40% by mass iron chloride solution, the copper foil was removed, washed with water, and dried in an oven at 80°C for 30 minutes to produce a cured film with a thickness of 50 μm.

[0197] <Prepreg production> The compositions obtained in the above Examples and Comparative Examples were impregnated into glass cloth (NE cloth, manufactured by Nitto Boseki), which was then dried at 100°C for 5 minutes and then at 140°C for 5 minutes to obtain prepregs.

[0198] <Impregnation into substrate> The produced prepreg was observed under magnification using a microscope (Keyence Corporation, VHX), and the impregnation ability was evaluated according to the following evaluation criteria. The results are shown in Table 4 or Table 5. When the following evaluation criteria are rated as "A," it can be said that the impregnation ability into the substrate is excellent.

[0199] -Evaluation criteria- A: When the prepreg is observed at a magnification of 200 times, no voids (gaps) or imperfections such as exposed glass cloth can be observed on the surface of the prepreg. B: When the prepreg was observed at a magnification of 200 times, imperfect impregnation such as voids or exposed glass cloth was observed. C: Poor impregnation was observed when the prepreg was observed at a magnification of less than 200x.

[0200] <Glass transition temperature (Tg)> Test pieces (width: 3 mm x length: 1 cm) were cut from the cured films prepared above, and measurements were performed using a dynamic viscoelasticity measuring device (Seiko Instruments Inc., model number: "EXSTAR4000") at a heating rate of 10°C / min from 50°C to 300°C at 1 Hz, and the tan δ measured at this time was taken as the glass transition temperature (Tg). When two or more tan δ values ​​were present, the lowest value was used as the Tg. The obtained Tg values ​​were evaluated according to the following evaluation criteria. The results are shown in Table 4 or Table 5. A rating of "A" or "B" according to the following evaluation criteria can be said to indicate excellent heat resistance.

[0201] -Evaluation criteria- A: The glass transition temperature (Tg) exceeds 180°C. B: The glass transition temperature (Tg) is greater than 150°C and equal to or less than 180°C. C: The glass transition temperature (Tg) is 150°C or lower.

[0202] <Peel strength> The thermoplastic resin compositions obtained in the above Examples and Comparative Examples were applied to copper foil (model number: CF-V9S-SV, manufactured by Fukuda Metals Co., Ltd.), heated at 100°C for 5 minutes, and then dried at 130°C for 5 minutes to form a coating film. Copper foil (model number: CF-V9S-SV, manufactured by Fukuda Metals Co., Ltd.) was placed on the resulting coating film, vacuum pressed at 150°C for 5 minutes, and then baked at 200°C for 2 hours under nitrogen to produce a cured film with copper foil (copper foil: 18 μm, cured film: 10 μm), which was used as a sample for peel strength testing.

[0203] A test piece (width: 5 mm x length: 10 cm) was cut from the prepared peel strength sample, and using a universal testing machine (Instron, model number: "Instron 5567"), the test piece (one copper foil and cured film laminate in the peel strength sample) was pulled at a 90-degree angle at 500 mm / min. The peel strength was measured in accordance with "IPC-TM-650 (Test Method (Test Method Manual)) 2.4.9" and evaluated according to the following evaluation criteria. The results are shown in Table 4 or Table 5. A rating of "A" or "B" in the following evaluation criteria indicates excellent adhesion.

[0204] -Evaluation criteria- S: Peel strength was 0.90 N / mm or more. A: The peel strength was 0.70 N / mm or more and less than 0.90 N / mm. B: The peel strength was 0.5 N / mm or more and less than 0.70 N / mm. C: The peel strength was less than 0.5 N / mm.

[0205] <Dielectric loss tangent (Df)> Test pieces (width: 6 cm x length: 6 cm) were cut out from the cured films prepared above, and the dielectric loss tangents of the test pieces at 10 GHz were measured using a cavity resonator method (TE mode resonator, dielectric constant measurement system, manufactured by AET Corporation), and the dielectric loss tangents were evaluated according to the following evaluation criteria. The results are shown in Table 4 or Table 5. A rating of "A" or "B" in the following evaluation criteria can be said to be excellent in low dielectric loss tangent.

[0206] -Evaluation criteria- A: The dielectric dissipation factor was less than 0.0015. B: The dielectric dissipation factor was 0.0015 or more and less than 0.0025. C: The dielectric dissipation factor was 0.0025 or more.

[0207] <CTI (Comparative Tracking Index): Comparative Tracking Index> The prepreg prepared above was cut into a width of 10 cm × a length of 10 cm, overlapped so that the thickness was 3 mm or more, sandwiched from both sides with a copper foil (model number: CF-V9S-SV, manufactured by Fukuda Metal Co., Ltd.), and fired at 200 °C for 2 hours to produce a CCL with copper foils on both sides. The obtained CCL with copper foils on both sides was immersed in a 40 mass% iron chloride solution, the copper foils were removed, then washed with water, and dried in an oven at 80 °C for 30 minutes to produce a cured film with a thickness of 3 mm or more, which was used as a sample for the comparative tracking index. The voltage of the sample for the comparative tracking index prepared above was measured using a tracking tester conforming to IEC (International Electrotechnical Commission) 60112, and the maximum voltage at which tracking did not occur was taken as the CTI value. The tracking resistance was evaluated according to the following evaluation criteria. The results are shown in Table 4 or Table 5. In the test, a 0.1 mass% aqueous ammonium chloride (NH4Cl) solution was used as the electrolyte.

[0208] - Evaluation Criteria - A: As a result of the tracking test, the maximum voltage at which tracking did not occur was 200 V or more. B: The maximum voltage at which tracking did not occur was 100 V or more and less than 200 V. C: The maximum voltage at which tracking did not occur was 100 V or less.

[0209] <Process Margin> Test pieces (width: 1 cm x length: 1 cm) were cut from the prepreg prepared above, and the melt viscosity was measured using a rotational rheometer (TA Instruments, model number: ARESG2) while the test pieces were heated from 70 to 200°C. The process margin was evaluated according to the following evaluation criteria. The results are shown in Table 4 or Table 5. When the following evaluation criteria are rated "A" or "B," the resin impregnated into the substrate (glass cloth) during prepreg preparation is easy to handle, and the amount of resin impregnated is also appropriately controlled, which means that the process margin is excellent.

[0210] -Evaluation criteria- A: The temperature range where the melt viscosity was below 1000 Pa·s was 40°C or higher. B: The temperature range in which the melt viscosity was 1000 Pa·s or less was 20°C or more and less than 40°C. C: The temperature range where the melt viscosity was 1000 Pa·s or less was less than 20°C.

[0211] [Table 4]

[0212] [Table 5]

[0213] <Chloride ion concentration> The polymer (A2) obtained in Synthesis Example 2 and dicumyl peroxide were mixed in a mixer rotor at a mass ratio of 99.5:0.5, and the concentration was adjusted with toluene to a solids concentration of 50 mass% to prepare a varnish (resin composition). The resulting varnish was applied to copper foil (model number: CF-T9DA-SV, manufactured by Fukuda Metal Foil & Powder Co., Ltd.) using a Baker-type applicator (gap: 125 μm), and then dried at 100°C for 5 minutes and then at 140°C for 5 minutes, followed by baking at 200°C for 2 hours under nitrogen. The copper foil was peeled off from the resulting cured film with copper foil, yielding a cured film with a thickness of 50 μm. Using this cured film, the chloride ion concentration contained in the polymer (A2) was measured in accordance with the Japan Printed Circuit Association's halogen-free copper clad laminate testing method (JPCA-ES01), and it was confirmed to be 600 ppm or less.

[0214] The resin compositions of Examples 1 to 13, 20 to 32, and 40 to 42 have superior impregnation into substrates compared to the resin compositions of Comparative Examples 1 to 4. Furthermore, it can be seen that the cured products obtained from the resin compositions of Examples 1 to 13, 20 to 32, and 40 to 42 have lower dielectric constants, lower dielectric loss tangents, superior tracking resistance, and process margins compared to the cured products obtained from the resin compositions of Comparative Examples 1 to 4.

Claims

1. (meth)acryloyloxy group and CH ２ a polymer (A) having at least one group selected from the group consisting of groups represented by =CR-*; Compound (B), a solvent (C); Contains R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, * represents a bonding site to another structure, the compound (B) is a hindered amine compound (B1) having no electron-withdrawing group other than a nitroxy radical group, and a hindered amine compound (B2) having an electron-withdrawing group other than a nitroxy radical group, The resin composition contains the hindered amine compound (B1) in an amount of 0.1 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the polymer (A).

2. The resin composition according to claim 1, wherein the polymer (A) is a polymer having a repeating unit represented by the following formula (1): 【Chemistry 1】 In formula (1), each X is independently —O—, —S—, or —N(R ３ )-, and R ３ is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, or a group in which a portion of such a hydrocarbon group or halogenated hydrocarbon group is substituted with at least one atom selected from an oxygen atom and a sulfur atom, and R １ is a divalent organic group, and R ２ is a divalent unsubstituted or substituted nitrogen-containing heteroaromatic ring.

3. The resin composition according to claim 1, wherein the polymer (A) is a polymer having a group represented by the following formula (a) at its terminal: 【Chemistry 2】 In formula (a), Y represents a group containing an ethylenically unsaturated double bond having 3 to 50 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an unsubstituted or substituted aliphatic hydrocarbon group having 6 to 50 carbon atoms, or an unsubstituted nitrogen-containing heteroaromatic ring, and when the aromatic hydrocarbon group or the aliphatic hydrocarbon group has a substituent, the substituent is a group other than a hydroxy group.

4. 2. The resin composition according to claim 1, further comprising a curable compound (D), wherein the content of the hindered amine compound (B1) is 0.01 parts by mass or more and 10 parts by mass or less relative to 100 parts by mass of the total content of the polymer (A) and the curable compound (D).

5. The resin composition according to claim 1, wherein the hindered amine compound (B1) is a compound represented by the following formula (B1-1): 【Transformation 3】

6. The resin composition according to claim 1, wherein the hindered amine compound (B2) is a compound represented by the following formula (B2-1): 【Chemistry 4】 In formula (B2-1), R Ｂ２１ represents an electron-withdrawing group other than a nitroxy radical group, n Ｂ２１ represents an integer of 1 to 6.

7. A cured product, which is a cured product of the resin composition according to any one of claims 1 to 6.

8. A laminate comprising a layer made of the cured product according to claim 7.

9. An electronic component comprising the laminate according to claim 8 .

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