Naphthylene ether resin, resin composition, cured article, prepreg, circuit board, build-up film, semiconductor sealing material, semiconductor device, method for producing naphthylene ether resin, and method for producing phenolic resin

Abstract

The present invention addresses the problem of providing: a naphthylene ether resin from which a cured article having excellent low dielectric properties and low elasticity properties can be obtained; a resin composition which contains the naphthylene ether resin; and a cured article which has excellent low dielectric properties and low elasticity properties. The solution to the problem is a naphthylene ether resin represented by general formula (1).

Description

Naphthylene ether resin, resin composition, cured product, prepreg, circuit board, build-up film, semiconductor encapsulant, semiconductor device, method for producing naphthylene ether resin, and method for producing phenolic resin.

[0001] This disclosure relates to naphthylene ether resin, resin composition, cured product, prepreg, circuit board, build-up film, semiconductor encapsulant, semiconductor device, method for producing naphthylene ether resin, and method for producing phenol resin.

[0002] In recent years, with the increase in the volume of information and communication, information communication in high-frequency bands has become widespread, and there is a demand for electrical insulating materials with superior electrical properties. In particular, there is a growing need for electrical insulating materials with low dielectric constant and low dielectric loss tangent in order to reduce transmission loss in high-frequency bands. In light of this trend, resins with radical curability and a low number of polar groups are attracting attention.

[0003] Against this backdrop, various curable resins containing vinyl groups with different chemical structures have been proposed. For example, Patent Document 1 below proposes a resin containing (meth)acryloyl groups at the ends of a naphthylene ether oligomer structure.

[0004] Japanese Patent Publication No. 2022-57344

[0005] However, although resins such as those disclosed in Patent Document 1 have been shown to have radical curability and high heat resistance, their low dielectric properties (low dielectric constant, low dielectric loss tangent) and low elastic properties need improvement.

[0006] Therefore, the object of this disclosure is to provide a naphthylene ether resin and a resin composition containing the naphthylene ether resin, as well as a cured product that is excellent in low dielectric properties and low elastic properties, that can solve the problems of the above-mentioned prior art.

[0007] As a result of intensive studies to solve the above problems, the present inventor has found that when a naphthylene ether resin having a radically polymerizable unsaturated group in the terminal substituent and having an aliphatic hydrocarbon structure as a polymerization unit is used as a cured product of a resin composition containing the resin, the cured product is excellent in low dielectric characteristics and low elastic characteristics, and has completed the present invention. The gist of the present invention for solving the above problems is as follows.

[0008] [1] A naphthylene ether resin represented by the following general formula (1). (In general formula (1), R and R １１ｂ each independently represent a radically polymerizable unsaturated group, L １１ and L １３ each independently represent a single bond or a divalent aliphatic hydrocarbon group, and one or more —CH ２ — of the aliphatic hydrocarbon group may be substituted with —CH(—OH)—, —O—, —C(═O)— or an arylene group which may have a substituent, L １２ represents a divalent aliphatic hydrocarbon group, and one or more —CH ２ — of the aliphatic hydrocarbon group may be substituted with —CH(—OH)—, —O—, —C(═O)— or an arylene group which may have a substituent, R １２ and R １４ each independently represent an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms, R １３ and R １５ each independently represent a hydroxyl group, a halogen atom, an alkoxy group, an alkyl group, an alkenyl group, or an aryl group, a and c are each independently an integer of 0 to 6, b and d are each independently an integer of 0 to 6, provided that the sum of a + b is at most 6 and the sum of c + d is at most 6, n is 1 to 20, provided that the molecule does not contain an —O—O— bond.)

[0009] [2] L in the general formula (1) １２The naphthylene ether resin described in [1], wherein each independently represents an alicyclic hydrocarbon group or a divalent aliphatic hydrocarbon group represented by the following general formula (2). (In general formula (2), L ２１ and L ２２ Each of these independently represents a divalent aliphatic hydrocarbon group, and A is a single bond or one or more -CH groups. ２ (- represents a divalent aliphatic hydrocarbon group which may be substituted with -CH(-OH)-, -O-, -C(=O)- or an optionally substituted arylene group, and * represents a bond, where A does not contain an -O-O- bond.)

[0010] [3] R in the general formula (1) １１ａ and R １１ｂ The naphthylene ether resin according to [1] or [2], wherein each is independently selected from the group consisting of an acryloyl group, a methacryloyl group, and a vinylphenyl group.

[0011] [4] L in the general formula (1) １２ The naphthylene ether resin according to any one of [1] to [3], wherein the number of carbon atoms is 7 or more.

[0012] [5] L in the general formula (1) １２ The naphthylene ether resin according to any one of [1] to [4], wherein the molecular weight per molecule is 98 or more.

[0013] [6] A naphthylene ether resin according to any one of [1] to [5], wherein dihydroxynaphthalene, a compound represented by the following general formula (3), and a compound having a radically polymerizable unsaturated group are used as reaction raw materials (I). (In general formula (3), L １２ represents a divalent aliphatic hydrocarbon group, and one or more -CH groups are present in the aliphatic hydrocarbon group. ２ - may be substituted with -CH(-OH)-, -O-, -C(=O)- or an arylene group which may have substituents, however L １２ (It does not contain an O-O bond.)

[0014] [7] A resin composition comprising the naphthylene ether resin described in any of [1] to [6].

[0015] [8] The resin composition according to [7], further comprising a maleimide resin.

[0016] [9] A cured product of the resin composition described in [7] or [8].

[0017]

[10] A prepreg having a reinforcing substrate and a semi-cured product of the resin composition described in [7] or [8] impregnated into the reinforcing substrate.

[0018]

[11] A circuit board which is a laminate of the prepreg and copper foil described in

[10] .

[0019]

[12] A build-up film containing the resin composition described in [7] or [8].

[0020]

[13] A semiconductor encapsulant containing the resin composition described in [7] or [8].

[0021]

[14] A semiconductor device comprising a cured product of the semiconductor encapsulant described in

[13] .

[0022]

[15] A method for producing a naphthylene ether resin according to any one of [1] to [6], comprising: (1) a step of reacting dihydroxynaphthalene with a compound represented by the following general formula (3) to obtain a phenol resin; and (2) a step of reacting the phenol resin with a compound having a radically polymerizable unsaturated group to obtain a naphthylene ether resin. (In general formula (3), L １２ represents a divalent aliphatic hydrocarbon group, and one or more -CH groups are present in the aliphatic hydrocarbon group. ２ - may be substituted with -CH(-OH)-, -O-, -C(=O)- or an arylene group which may have substituents, however L １２ (It does not contain an O-O bond.)

[0023]

[16] A method for producing a phenol resin, comprising reacting dihydroxynaphthalene with a compound represented by the following general formula (3). (In general formula (3), L １２ represents a divalent aliphatic hydrocarbon group, and one or more -CH groups are present in the aliphatic hydrocarbon group. ２- may be substituted with -CH(-OH)-, -O-, -C(=O)- or an arylene group which may have substituents, however L １２ (It does not contain an O-O bond.)

[0024] According to this disclosure, it is possible to provide a naphthylene ether resin capable of producing a cured product with excellent low dielectric properties and low elastic properties, a resin composition containing the naphthylene ether resin, and a cured product with excellent low dielectric properties and low elastic properties.

[0025] Figure 1 shows the GPC chart of the phenolic resin (A-1) synthesized in Synthesis Example 1. Figure 2 shows the GPC chart of the phenolic resin (A-1) synthesized in Synthesis Example 1. １３ Figure 3 shows the 13C-NMR spectrum. Figure 4 shows the GPC chart of the phenol resin (A-1) synthesized in Synthesis Example 1. Figure 5 shows the GPC chart of the phenol resin (A-2) synthesized in Synthesis Example 2. Figure 6 shows the GPC chart of the phenol resin (A-3) synthesized in Synthesis Example 3. Figure 7 shows the GPC chart of the phenol resin (A-4) synthesized in Synthesis Example 4. Figure 8 shows the GPC chart of the methacrylate resin (B-1) synthesized in Synthesis Example 6. Figure 9 shows the GPC chart of the methacrylate resin (B-2) synthesized in Synthesis Example 7. Figure 10 shows the GPC chart of the vinylbenzyl-terminated resin (B-3) synthesized in Synthesis Example 8. Figure 11 shows the GPC chart of the methacrylate resin (B-4) synthesized in Synthesis Example 9. Figure 12 shows the GPC chart of the vinylbenzyl-terminated resin (B-5) synthesized in synthesis example 10.

[0026] The naphthylene ether resin, resin composition, cured product, prepreg, circuit board, build-up film, semiconductor encapsulant, semiconductor device, and method for producing the naphthylene ether resin of the present invention will be described in detail below based on embodiments thereof.

[0027] <Terminology> Unless otherwise specified in this specification, the following terms may be applied. In this specification, "reaction material" refers to a compound used to obtain a target compound by a chemical reaction such as combination or decomposition, and which partially constitutes the chemical structure of the target compound. Substances that act as aids to chemical reactions, such as solvents and catalysts, are excluded. In this specification, "aromatic group" preferably has an aromatic ring having 3 to 30 carbon atoms, and more preferably has an aromatic ring having 4 to 26 carbon atoms. Furthermore, in this specification, the hydrogen atoms of the aromatic ring in the aromatic group may be substituted with substituents, such as alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, or halogen atoms. In addition, "aromatic group" may include heteroaromatic compounds, and the "-CH" in the "aromatic group" is included. ２The - or -CH= may be substituted with -O-, -S-, or -N= so that they are not adjacent to each other. Examples of the types of aromatic rings include monocyclic aromatic rings, fused aromatic rings, and ring-assembled aromatic rings. Examples of monocyclic aromatic rings include benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, and triazine. Examples of fused aromatic rings include naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, and acridine. Examples of ring-assembled aromatic rings include biphenyl, binaphthalene, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, and quaterphenyl. Furthermore, the hydrogen atoms of the aromatic ring in the aromatic group may be substituted with, for example, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom. A monovalent aromatic group refers to an aromatic group from which one hydrogen atom has been removed. In this specification, the term "aliphatic hydrocarbon group" refers to a group from which one or more hydrogen atoms bonded to the aliphatic carbon of an aliphatic compound have been removed. More specifically, a monovalent aliphatic hydrocarbon group refers to a group from which one hydrogen atom bonded to the aliphatic carbon of an aliphatic compound has been removed, and a divalent aliphatic hydrocarbon group refers to a group from which two hydrogen atoms bonded to the aliphatic carbon of an aliphatic compound have been removed. In addition, in this specification, an "aliphatic hydrocarbon group" refers to a group whose main chain is an aliphatic hydrocarbon, and which may have an aromatic ring or the like in part. Examples of divalent aliphatic hydrocarbon groups include optionally substituted alkylene groups, optionally substituted cycloalkylene groups, optionally substituted alkenylene groups, optionally substituted cycloalkenylene groups, and optionally substituted alkapolienylene groups (preferably 2 to 10, more preferably 2 to 6, even more preferably 2 to 4, and even more preferably 2 double bonds).In this specification, unless otherwise specified, the number of carbon atoms in an aliphatic hydrocarbon group is preferably 1 or more, more preferably 2 or more, even more preferably 3 or more, 4 or more, 5 or more, or 6 or more, preferably 50 or less, more preferably 40 or less, even more preferably 30 or less, 20 or less, 18 or less, 16 or less, 14 or less, or 12 or less. The number of carbon atoms in substituents is not included in this number of carbon atoms. In this specification, "alkyl group" may be linear, branched, or cyclic, and examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, isohexyl group, (n-)heptyl group, (n-)octyl group, (n-)nonyl group, (n-)decyl group, (n-)undecyl group, (n-)dodecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, norbornyl group, or adamantyl group. In this specification, "cycloalkyl group" refers to a cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, norbornyl group, or adamantyl group, etc. In this specification, "alkylthio group" refers to a methylthio group, ethylthio group, propylthio group, butylthio group, octylthio group, or 2-ethylhexylthio group, etc. In this specification, "alkenyl group" refers to an ethynyl group, 1-propynyl group, 2-propynyl group, 2-butynyl group, pentynyl group, hexynyl group, vinyl group, allyl group, or isopropenyl group, etc. In addition, "alkenylene group" refers to a divalent group obtained by removing one arbitrary hydrogen atom from the above-mentioned "alkenyl group". In this specification, "alkoxy group" refers to, for example, a methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, pentyloxy group, hexyloxy group, 2-ethylhexyloxy group, octyloxy group, or nonyloxy group.Examples of "aryl groups" in this specification include phenyl groups, naphthyl groups, phenalenyl groups, phenantrenyl groups, anthryl groups, azulenyl groups, indenyl groups, indanyl groups, and tetralinyl groups. Furthermore, the hydrogen atoms of the aromatic ring in the aryl group may be substituted with, for example, a C1-C10 alkyl group, a C1-C10 alkoxy group, or a halogen atom. Examples of "aralkyl groups" in this specification include benzyl groups, diphenylmethyl groups, biphenyl groups, and naphthylmethyl groups. The hydrogen atoms of the aromatic ring in the aralkyl group may be substituted with, for example, a C1-C10 alkyl group, a C1-C10 alkoxy group, or a halogen atom. Examples of "aryloxy groups" in this specification include phenoxy groups, naphthyloxy groups, anthuryloxy groups, phenanthryloxy groups, or pyrenyloxy groups. In this specification, "arylthio group" refers to arylthio groups such as phenylthio group, naphthylthio group, anthrylthio group, phenanthrylthio group, or pyrenylthio group. In this specification, "halogen atom" refers to, for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. In this specification, "alkylene group" refers to, for example, a methylene group, an ethylene group, a propylene group, a 1-methylmethylene group, a 1,1-dimethylmethylene group, a 1-methylethylene group, a 1,1-dimethylethylene group, a 1,2-dimethylethylene group, a propylene group, a butylene group, a 1-methylpropylene group, a 2-methylpropylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, and the like.In this specification, "alkylene oxy group" refers to, for example, oxymethylene group, oxypropylene group, oxy(1-methylmethylene) group, oxy(1,1-dimethylmethylene) group, oxy(1-methylethylene) group, oxy(1,1-dimethylethylene) group, oxy(1,2-dimethylethylene) group, oxybutylene group, oxy(1-methylpropylene) group, oxy(2-methylpropylene) group, oxypentylene group, oxyhexylene group, oxyheptylene group, oxyoctylene group, oxynonylene group, oxydecylen group, oxyundecylen group, oxidedodecylen group, etc. In this specification, "hydrocarbon group" refers to a monovalent group and includes linear, branched, or cyclic saturated hydrocarbons, unsaturated hydrocarbons, or aromatic groups. For example, the "hydrocarbon group" is one group selected from the group consisting of alkyl groups (e.g., the above alkyl groups), alkenyl groups (e.g., the above alkenyl groups), aryl groups (e.g., the above aryl groups), aryloxy groups (e.g., the above aryloxy groups), aralkyl groups (e.g., the above aralkyl groups), and alkoxy groups (e.g., the above alkoxy groups), and one or more -CH groups in the said group. ２ The -s may be substituted with -O-, -C(=O)-, or -S- so as not to be adjacent to each other, or one or more -CH groups in the alkyl group. ２ -CH ２ The hyphens may be substituted with -CH=CH- so that they are not adjacent to each other. In this specification, "arylene group" means a divalent aromatic hydrocarbon group. Examples of arylene groups include 1,4-phenylene group, 1,3-phenylene group, 1,2-phenylene group, 1,4-naphthylene group, 1,5-naphthylene group, 1,8-naphthylene group, 4,4'-biphenylene group, and the like.

[0028] <Naphthylene ether resin> The naphthylene ether resin of this embodiment is characterized by being represented by the following general formula (1). (In general formula (1), R １１ａ and R １１ｂ Each of these independently represents a radically polymerizable unsaturated group, L １１ and L １３Each of these independently represents a single bond or a divalent aliphatic hydrocarbon group, and one or more -CH groups of the aliphatic hydrocarbon group ２ - may be substituted with -CH(-OH)-, -O-, -C(=O)- or an arylene group which may have substituents, L １２ represents a divalent aliphatic hydrocarbon group, and one or more -CH groups are present in the aliphatic hydrocarbon group. ２ - may be substituted with -CH(-OH)-, -O-, -C(=O)- or an arylene group which may have substituents, R １２ and R １４ Each of these independently represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, an aryl group having 1 to 20 carbon atoms, an aralkyl group having 1 to 20 carbon atoms, or an aryloxy group having 1 to 20 carbon atoms. １３ and R １５ Each of the following independently represents a hydroxyl group, halogen atom, alkoxy group, alkyl group, alkenyl group, or aryl group; a and c are each independently integers from 0 to 6; b and d are each independently integers from 0 to 6, provided that the sum of a + b is a maximum of 6, and the sum of c + d is a maximum of 6; n is from 1 to 20, provided that the molecule does not contain an -O-O- bond.

[0029] The naphthylene ether resin represented by the above general formula (1) (hereinafter sometimes referred to as "the naphthylene ether resin of this embodiment") has low dielectric properties due to having a nonpolar condensed carbon ring and a radically polymerizable unsaturated group at the terminal substituent. Furthermore, the naphthylene ether resin of this embodiment has a flexible aliphatic hydrocarbon structure in its polymerization unit, which reduces its elastic modulus and results in low elastic properties. As a result, when a resin composition containing the naphthylene ether resin of this embodiment is cured, the cured product of the resin composition exhibits excellent low dielectric and low elastic properties. In addition, the naphthylene ether resin of this embodiment has high heat resistance due to having multiple naphthylene ether structures. More specifically regarding the low dielectric properties, because it has a nonpolar condensed carbon ring and a radically polymerizable unsaturated group at the terminal substituent, it can copolymerize with radically curable compounds that have low polarity compared to resins with relatively high polarity such as epoxy resins, and can be used in combination with various compounds, making it possible to obtain a cured product with excellent low dielectric properties. Furthermore, the naphthylene ether resin of this embodiment has low hygroscopicity and excellent low dielectric properties after moisture absorption.

[0030] In the above general formula (1), R １１ａ and R １１ｂ Each of these independently represents a radically polymerizable unsaturated group. A radically polymerizable unsaturated group represents a group containing an unsaturated bond that exhibits radical polymerizability. Examples of radically polymerizable unsaturated groups include acryloyl group, methacryloyl group, vinylphenyl group, vinyl group, allyl group, isopropenyl group, 1-propenyl group, styrylmethyl group, maleimide group, alkenyloxycarbonyl group (e.g., vinyloxycarbonyl group), or alkyl groups substituted with alkenyloxycarbonyl groups (e.g., CH ２ Examples include =CH-O-C(=O)-Y-(where Y is, for example, an alkylene group having 1 to 5 carbon atoms)), vinyl ether groups, etc. Among these, the radical polymerizable unsaturated group is preferably selected from the group consisting of acryloyl group, methacryloyl group, and vinylphenyl group, and more preferably a methacryloyl group or a vinylphenyl group.

[0031] In the above general formula (1), L １１ and L １３ Each of these independently represents a single bond or a divalent aliphatic hydrocarbon group. １１ and / or L １３ When is a divalent aliphatic hydrocarbon group, one or more -CH groups are present in the aliphatic hydrocarbon group. ２ The - may be substituted with -CH(-OH)-, -O-, -C(=O)-, or an arylene group which may have substituents. However, L １１ and L １３ This excludes the -O-O- bond. １１ and L １３ is a terminal substituent (R １１ａ , R １１ｂ The type of terminal substituent (R) can determine whether it is a single bond or a divalent aliphatic hydrocarbon group. １１ａ , R １１ｂ ) If L is an acryloyl group or a methacryloyl group １１ and L １３ It is preferable that each of these can be a single bond. Also, for example, terminal substituents (R １１ａ , R １１ｂ If ) is a vinylphenyl group, L １１ and L １３ Preferably, it can be a divalent aliphatic hydrocarbon group, and more specifically, it is preferable that it be a divalent aliphatic hydrocarbon group having 1 carbon atom.

[0032] L １１ and L １３ If is a divalent aliphatic hydrocarbon group, the number of carbon atoms in the divalent aliphatic hydrocarbon group may be 1 or more, for example, 3 or more, 5 or more, 7 or more, or 9 or more, or 50 or less, 45 or less, 40 or less, 36 or less, 20 or less, 15 or less, or 10 or less. These upper and lower limits can be combined in any way.

[0033] In the above general formula (1), L １２ Each of these independently represents a divalent aliphatic hydrocarbon group, and the aliphatic hydrocarbon group contains one or more -CH ２The - may be substituted with -CH(-OH)-, -O-, -C(=O)-, or an arylene group which may have substituents. The divalent aliphatic hydrocarbon group may be linear, branched, or cyclic, and may have one or more unsaturated bonds. The divalent aliphatic hydrocarbon group is preferably, for example, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, and a dodecylene group. In the above general formula (1), L １２ The number of carbon atoms is not particularly limited, but from the viewpoint of low elasticity, it is preferable that the number of carbon atoms be 1 or more, 3 or more, 5 or more, 7 or more, 8 or more, 9 or more, 12 or more, 16 or more, and 20 or more. Also, L １２ The upper limit of the number of carbon atoms is not particularly limited, but may be, for example, 50 or less, 45 or less, 40 or less, or 36 or less. These upper and lower limits can be combined arbitrarily. １２ The range of the number of carbon atoms is preferably 3 to 50, preferably 5 to 45, preferably 7 to 40, preferably 8 to 36, preferably 9 to 36, preferably 12 to 36, preferably 16 to 36, and preferably 20 to 36.

[0034] In general formula (1), there are n L １２ Of these, L １２ The molecular weight per unit is preferably 14 or more. From the viewpoint of reducing the elastic modulus of the cured resin, L １２ The molecular weight per molecule is more preferably 98 or higher, and even more preferably 112 or higher. １２ The upper limit of the molecular weight per molecule is not particularly limited, but it may be 1000 or less, or 800 or less. These upper and lower limits can be combined arbitrarily. １２ The range of molecular weight per molecule is L１２ The molecular weight per molecule is more preferably 98 to 1000, and even more preferably 112 to 800.

[0035] In general formula (1), L １２ Preferably, each of these independently represents an alicyclic hydrocarbon group or a divalent aliphatic hydrocarbon group represented by the following general formula (2). (In general formula (2), L ２１ and L ２２ Each of the above independently represents a divalent aliphatic hydrocarbon group, and A represents a single bond or a divalent aliphatic hydrocarbon group, provided that the aliphatic hydrocarbon group contains one or more -CH ２ The - may be substituted with -CH(-OH)-, -O-, -C(=O)-, or an arylene group which may have a substituent, and * represents a bond, where A does not contain an -O-O- bond.

[0036] Said L １２ The alicyclic hydrocarbon group is not particularly limited and may be a divalent alicyclic hydrocarbon group having 3 to 36 carbon atoms. Examples of alicyclic hydrocarbon groups include monocyclic hydrocarbon groups such as cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, cycloheptyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl; and polycyclic hydrocarbon groups such as dicyclopentanyl, dicyclopentenyl, tricyclodecanyl, adamantyl, and isobornyl.

[0037] In general formula (2), L ２１ and L ２２Each independently represents a divalent aliphatic hydrocarbon group. The divalent aliphatic hydrocarbon group may be any of a straight-chain one, one having a branched structure, one having an unsaturated bond, and one having a cyclic structure. Also, the number of carbon atoms of the divalent aliphatic hydrocarbon group is not particularly limited, but may be, for example, 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more. Further, the number of carbon atoms of the divalent aliphatic hydrocarbon group may be 40 or less, 35 or less, 30 or less, 25 or less, or 20 or less. These upper and lower limits can be arbitrarily combined. As the divalent aliphatic hydrocarbon group, for example, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, or a dodecylene group is preferable.

[0038] In general formula (2), A represents a single bond or one or more —CH ２ — that is optionally substituted with —CH(—OH)—, —O—, —C(═O)— or an arylene group that may have a substituent, provided that A does not contain an —O—O— bond. The divalent aliphatic hydrocarbon group of A is synonymous with the divalent aliphatic hydrocarbon groups of L ２１ and L ２２ . As the arylene group, for example, a 1,4-phenylene group, a 1,3-phenylene group, a 1,2-phenylene group, a 1,4-naphthylene group, a 1,5-naphthylene group, a 1,8-naphthylene group, or a 4,4′-biphenylene group is preferable.

[0039] In general formula (2), * represents a bond.

[0040] In general formula (1), R １２ and R １４ each independently represent an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms. Among these, it is preferable that R １２ and R １４ represent an aryl group having 6 to 20 carbon atoms. R １２ and R １４Due to the bulky structure such as an aryl group, etc., it is presumed that the molecular rigidity increases, molecular motion is suppressed, and the improvement of the glass transition temperature (Tg) can be more effectively demonstrated. When a and c are integers of 2 or more, a plurality of R １２ and R １４ may be the same as each other or different from each other. [[ID=�]] <००००२८२> R １２ and R １４ alkyl groups having 1 to 20 carbon atoms are preferably alkyl groups having 1 to 15 carbon atoms, more preferably alkyl groups having 1 to 10 carbon atoms, and even more preferably alkyl groups having 1 to 6 carbon atoms. R １２ and R １４ alkyl groups having 1 to 20 carbon atoms may be linear or branched, and for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, isohexyl group, (n-)heptyl group, (n-)octyl group, (n-)nonyl group, (n-)decyl group, (n-)undecyl group, or (n-)dodecyl group are preferred.

[0042] R​​​​​​​​​​​​​​​​​１４ As the aryl group having 6 to 20 carbon atoms, for example, phenyl, naphthyl, phenalenyl, phenantrenyl, anthryl, azlenyl, indenyl, indanyl, or tetralinyl groups are preferred.

[0044] R １２ and R １４ The aralkyl group having 7 to 20 carbon atoms is preferably an aralkyl group having 7 to 19 carbon atoms, and more preferably an aralkyl group having 7 to 15 carbon atoms. １２ and R １４ As the aralkyl group having 7 to 20 carbon atoms, for example, benzyl group, diphenylmethyl group, biphenyl group, or naphthylmethyl group are preferred.

[0045] R １２ and R １４ The aryloxy group having 6 to 20 carbon atoms is preferably an aryloxy group having 6 to 18 carbon atoms, and more preferably an aryloxy group having 6 to 14 carbon atoms. １２ and R １４ As the aryloxy group having 6 to 20 carbon atoms, for example, phenoxy, naphthyloxy, anthuryloxy, phenanthryloxy, or pyrenyloxy groups are preferred.

[0046] In general formula (1), R １３ and R １５ Each of these independently represents a hydroxyl group, halogen atom, alkoxy group, alkyl group, alkenyl group, or aryl group. Specific examples of halogen atoms, alkoxy groups, alkyl groups, alkenyl groups, and aryl groups are given in the glossary section. When b and d are integers of 2 or more, there are multiple R １３ and R １５ They may be the same as or different from each other.

[0047] In general formula (1), a and c are each independent integers from 0 to 6, preferably from 1 to 4, more preferably from 1 to 2, and particularly preferably 1.

[0048] In general formula (1), b and d are each independent integers between 0 and 6, preferably between 0 and 4, and more preferably between 0 and 2.

[0049] In general formula (1), the sum of a + b is at most 6, and the sum of c + d is at most 6.

[0050] In general formula (1), n ​​represents the average number of repeating units. In general formula (1), n ​​is between 1 and 20, preferably between 1 and 10, and more preferably between 1 and 8. The average number of repeating units can be calculated from the charge ratio, NMR, GPC, etc.

[0051] In general formula (1), the bonding positions of the two oxygen atoms to each naphthalene ring are not particularly limited, but examples include positions 2 and 7, 1 and 4, and 1 and 5 of the naphthalene ring. In general formula (1), the bonding positions of the naphthalene ring and the two oxygen atoms may differ for each naphthalene ring.

[0052] The naphthylene ether resin of this embodiment is preferably a resin in which dihydroxynaphthalene, a compound represented by the following general formula (3), and a compound having a radically polymerizable unsaturated group are used as reaction raw materials (I). (In general formula (3), L １２ represents a divalent aliphatic hydrocarbon group, and one or more -CH groups are present in the aliphatic hydrocarbon group. ２ - may be substituted with -CH(-OH)-, -O-, -C(=O)- or an arylene group which may have substituents, however L １２ (This compound does not contain an O-O bond.) By using the compound represented by the above general formula (3), which is a diol, as the reaction raw material for the naphthylene ether resin in this embodiment, the range of materials to choose from is broader compared to using alkyl halides or the like as the material derived from the aliphatic hydrocarbon group, and a wide range of resins (for example, resins with a larger number of carbon atoms in the aliphatic hydrocarbon group) can be produced. Furthermore, compared to using alkyl halides as the reaction raw material for the naphthylene ether resin, it is industrially preferable in terms of cost reduction and other factors.

[0053] L in general formula (3) １２ L is in general formula (1) １２ This corresponds to L in general formula (3). １２ L is in general formula (1) １２ We will use the explanation regarding this matter.

[0054] Specific examples of compounds represented by general formula (3) are, but are not limited to, 1,2-ethanediol (ethylene glycol), 1,2-propanediol (propylene glycol), 1,4-butanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, and 18,18'-oxybis[(9Z,12Z)-9,12-octadecadiene-1-ol].

[0055] The compound represented by general formula (3) preferably has a hydroxyl group equivalent of 32 or more and 3000 or less, and more preferably 32 or more and 2000 or less. The hydroxyl group equivalent can be measured by a method in accordance with the neutralization titration method specified in JIS K0070 (1992).

[0056] Examples of the above-mentioned dihydroxynaphthalenes include 2,7-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, and 1,6-dihydroxynaphthalene.

[0057] The compounds having the radically polymerizable unsaturated group described above are not particularly limited as long as they have a radically polymerizable unsaturated group, but ethylenically unsaturated groups having a carbon-carbon double bond at the terminal or internally are preferred. Specifically, these may be compounds having unsaturated aliphatic groups such as vinyl groups, allyl groups, and 3-cyclohexenyl groups; unsaturated aliphatic group-containing aromatic groups such as vinylphenyl groups (p-vinylphenyl groups, m-vinylphenyl groups) and styryl groups; acryloyl groups, methacryloyl groups, maleoyl groups (maleimide groups when imidized), alkenyloxycarbonyl groups (e.g., vinyloxycarbonyl groups) or alkyl groups substituted with alkenyloxycarbonyl groups, or α,β-unsaturated carbonyl groups such as fumaroyl groups. Compounds having a radically polymerizable unsaturated group preferably have one or more radically polymerizable unsaturated groups, and more preferably have two or more.

[0058] Specific examples of compounds having the above-mentioned radical polymerizable unsaturated group include, but are not limited to, (meth)acrylic acid halides such as acrylic acid chloride or methacrylic acid chloride, acid anhydrides such as acrylic anhydride or methacrylic anhydride, vinyl benzyl halides or vinyl aralkyl halides such as chloromethylstyrene, aryl halides having an alkenyl group (or alkenyl group-containing aromatic halides), or (meth)allyl halides such as allyl chloride, allyl bromide, methallyl chloride, or methallyl bromide.

[0059] - Physical Properties of Naphthylene Ether Resin - The naphthylene ether resin of this embodiment preferably has a number-average molecular weight (Mn) in the range of 350 to 10,000, and more preferably in the range of 400 to 8,000. Furthermore, the weight-average molecular weight (Mw) of the naphthylene ether resin of this embodiment preferably has a range of 400 to 500,000, and more preferably in the range of 450 to 400,000. The number-average molecular weight (Mn) and weight-average molecular weight (Mw) can be measured by gel permeation chromatography (GPC).

[0060] The softening point of the naphthylene ether resin in this embodiment is preferably 200°C or lower, and more preferably 150°C or lower. A softening point within this range is preferable because it provides excellent moldability. The softening point here is measured according to JIS K7234 (ring-ball method).

[0061] (Method for producing naphthylene ether resin) The method for producing naphthylene ether resin according to this embodiment will now be described. The method for producing naphthylene ether resin according to this embodiment includes: step (1) (hereinafter also simply referred to as "step (1)"), in which dihydroxynaphthalene is reacted with a compound represented by the following general formula (3) to obtain a phenol resin; and step (2) (hereinafter also simply referred to as "step (2)"), in which the phenol resin is reacted with a compound having a radically polymerizable unsaturated group to obtain a naphthylene ether resin. (In general formula (3), L １２ represents a divalent aliphatic hydrocarbon group, and one or more -CH groups are present in the aliphatic hydrocarbon group. ２ - may be substituted with -CH(-OH)-, -O-, -C(=O)- or an arylene group which may have substituents, however L １２ (It does not contain an O-O bond.)

[0062] In the above general formula (3), L １２ L is in general formula (1) １２ This is synonymous with L in general formula (1). １２ The above explanation will be applied to this matter. In other words, one example of a method for producing naphthylene ether resin in this embodiment is to first produce a phenol resin as a precursor of naphthylene ether resin (step (1)), and then react the phenol resin with a compound having a radically polymerizable unsaturated group (step (2)) to obtain the target naphthylene ether resin. After describing preferred embodiments of each step in the series of steps for producing naphthylene ether resin, the method for producing the precursor phenol resin will also be mentioned.

[0063] [Step (1)] In the method for producing naphthylene ether resin of this embodiment, step (1) is a step of reacting dihydroxynaphthalene with the compound represented by the general formula (3) above to obtain a phenol resin, which is a precursor of the target naphthylene ether resin. The dihydroxynaphthalene and the compound represented by the general formula (3) used in step (1) are the same as the dihydroxynaphthalene and the compound represented by the general formula (3) in the reaction raw materials for the naphthylene ether resin of this embodiment, and the explanation of dihydroxynaphthalene and the compound represented by the general formula (3) in the naphthylene ether resin of this embodiment will be used with reference.

[0064] In step (1), the phenolic resin obtained can be represented by the following general formula (4). (In general formula (4), L １２ represents a divalent aliphatic hydrocarbon group, and one or more -CH groups are present in the aliphatic hydrocarbon group. ２ - may be substituted with -CH(-OH)-, -O-, -C(=O)- or an arylene group which may have substituents, R １２ and R １４ Each of these independently represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, an aryl group having 1 to 20 carbon atoms, an aralkyl group having 1 to 20 carbon atoms, or an aryloxy group having 1 to 20 carbon atoms. １３ and R １５ Each of the following independently represents a hydroxyl group, halogen atom, alkoxy group, alkyl group, alkenyl group, or aryl group; a and c are each independently integers from 0 to 6; b and d are each independently integers from 0 to 6, provided that the sum of a + b is a maximum of 6, and the sum of c + d is a maximum of 6; n is from 1 to 20, provided that the molecule does not contain an -O-O- bond.

[0065] The phenol resin obtained in step (1) preferably has a hydroxyl group equivalent of 170 to 5000, and more preferably 200 to 4000. The hydroxyl group equivalent can be measured by a method in accordance with the neutralization titration method specified in JIS K0070 (1992).

[0066] The reaction conditions in step (1) can be set as appropriate. For example, condensation may be carried out under an acid catalyst at a temperature of 50 to 250°C for 1 to 20 hours while stirring.

[0067] Examples of acid catalysts used in step (1) include inorganic acids such as phosphoric acid, sulfuric acid, and hydrochloric acid; toluenesulfonic acids such as oxalic acid, benzenesulfonic acid, and p-toluenesulfonic acid; organic acids such as methanesulfonic acid and fluoromethanesulfonic acid; and Friedel-Crafts catalysts such as aluminum chloride, zinc chloride, stannous chloride, ferric chloride, and diethylsulfuric acid. These may be used individually or in combination of two or more types.

[0068] The amount of these acid catalysts used is preferably in the range of 0.01 to 5.0 parts by mass per 100 parts by mass of dihydroxynaphthalene in the case of inorganic acids and organic acids.

[0069] Step (1) may be carried out using an aralkylating agent. Examples of aralkylating agents include halide compounds such as benzyl chloride, benzyl bromide, benzyl iodite, o-methylbenzyl chloride, m-methylbenzyl chloride, p-methylbenzyl chloride, p-ethylbenzyl chloride, p-isopropylbenzyl chloride, p-tert-butylbenzyl chloride, p-phenylbenzyl chloride, 5-chloromethylacenaphthylene, 2-naphthylmethyl chloride, 1-chloromethyl-2-naphthalene and their nuclear substituted isomers, α-methylbenzyl chloride, and α,α-dimethylbenzyl chloride; benzyl methyl ether, o-methylbenzyl methyl ether, m-methylbenzyl methyl ether, p-methylbenzyl methyl ether, p-ethylbenzyl methyl ether and their nuclear substituted isomers Examples include ether compounds such as benzyl ethyl ether, benzyl propyl ether, benzyl isobutyl ether, benzyl n-butyl ether, p-methylbenzyl methyl ether and their nuclear-substituted isomers; alcohol compounds such as benzyl alcohol, o-methylbenzyl alcohol, m-methylbenzyl alcohol, p-methylbenzyl alcohol, p-ethylbenzyl alcohol, p-isopropylbenzyl alcohol, ptert-butylbenzyl alcohol, p-phenylbenzyl alcohol, α-naphthylmethanol and their nuclear-substituted isomers, α-methylbenzyl alcohol, and α,α-dimethylbenzyl alcohol; and styrene compounds such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, and β-methylstyrene. These may be used individually or in combination of two or more. Among these, benzyl chloride, benzyl bromide, and benzyl alcohol are preferred because they yield resins with excellent dielectric properties and moisture resistance and solderability in the cured product.

[0070] The reaction ratio of dihydroxynaphthalene to the aralkylating agent is preferably such that the molar ratio of the two [dihydroxynaphthalene / aralkylating agent] is 1.0 / 0.1 to 1.0 / 6.0, as this yields a naphthylene ether resin with excellent flame retardancy, moisture resistance, and solderability in the cured product.

[0071] Step (1) may be carried out in an organic solvent if necessary. Examples of organic solvents used here include ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; acetic acid ester solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitol solvents such as cellosolve and butyl carbitol; aromatic hydrocarbon solvents such as toluene and xylene; dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. These may be used individually or as a mixture of two or more solvents.

[0072] In step (1), the ratio of dihydroxynaphthalene to the compound represented by the general formula (3) above (dihydroxynaphthalene: compound represented by the general formula (3) above) is preferably 100:50 to 100:90 in molar ratio.

[0073] In step (1), neutralization may be carried out after the reaction using a basic aqueous solution or the like, if necessary. Alternatively, after the reaction, the catalyst salt may be removed by washing with water, and low molecular weight products may be removed by heating and reduced pressure.

[0074] [Step (2)] In the method for producing naphthylene ether resin of this embodiment, step (2) is a step of reacting the phenol resin, which is a precursor obtained in step (1), with a compound having a radically polymerizable unsaturated group to obtain naphthylene ether resin. The phenol resin is as described in step (1). The compound having a radically polymerizable unsaturated group is synonymous with the compound having a radically polymerizable unsaturated group in the reaction raw materials for the naphthylene ether resin of this embodiment, and the explanation regarding the compound having a radically polymerizable unsaturated group in the naphthylene ether resin of this embodiment can be applied.

[0075] The reaction conditions for the phenol resin obtained in step (1) and the compound having a radically polymerizable unsaturated group are not particularly limited, but for example, one method is to charge both in any proportion into a reaction vessel and react them for several hours under temperature conditions of 20 to 120°C. Specifically, the reaction can be carried out by using alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate, sodium bicarbonate and potassium carbonate, and aqueous solutions thereof, or Lewis bases such as tertiary amines and pyridines as catalysts. These catalysts are appropriately selected from the viewpoint of the characteristics of the compound having a radically polymerizable unsaturated group, raw material costs and reaction rate, and both may be used in combination. When using these catalysts, it is preferable to use an excess of basic catalyst compared to the acid that is compounded, since the hydrogen chloride and carboxylic acid compounded by the reaction deactivate them by forming salts. After the reaction is complete, the by-product catalyst residue can be purified and removed by methods such as washing with water or filtration. The reaction may also be carried out in a solvent as needed, and any catalyst may be used. After the reaction is complete, purification operations such as washing with water may be performed as needed.

[0076] The solvent can be any solvent that is appropriate and suitable depending on the solubility of the reaction raw materials and the reaction temperature. Examples include ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; acetic acid ester solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; aromatic hydrocarbon solvents such as toluene and xylene; and dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. These may be used individually or in combination of two or more. The amount of solvent used is preferably in the range of 100 to 500% by mass relative to the total mass of the reaction raw materials.

[0077] The catalyst can be one of publicly known and conventional types. For example, when (meth)acrylic acid halide or (meth)acrylic anhydride is used as a raw material, it is preferable to use a pyridine-based catalyst under basic conditions with a tertiary amine such as triethylamine added, as this provides excellent catalytic activity. From a cost viewpoint, triethylamine is preferred as the tertiary amine, and dimethylaminopyridine is preferred as the pyridine-based catalyst due to its high activity. Furthermore, when organic halides such as chloromethylstyrene and (meth)allyl halide are used as raw materials, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate, sodium bicarbonate, and potassium carbonate, and aqueous solutions thereof can also be suitably used.

[0078] In step (2), the ratio of the phenol resin obtained in step (1) to the compound having radically polymerizable unsaturated groups (phenol resin obtained in step (1): compound having radically polymerizable unsaturated groups) is preferably 1.0:1.0 to 1.0:2.0 in terms of the functional group equivalent ratio of hydroxyl groups in the phenol resin to the compound having radically polymerizable unsaturated groups.

[0079] (Method for producing phenolic resin) The disclosure also relates to a method for producing phenolic resin. The method for producing phenolic resin according to the disclosure is characterized by reacting dihydroxynaphthalene with a compound represented by the following general formula (3). (In general formula (3), L １２ represents a divalent aliphatic hydrocarbon group, and one or more -CH groups are present in the aliphatic hydrocarbon group. ２ - may be substituted with -CH(-OH)-, -O-, -C(=O)- or an arylene group which may have substituents, however L １２ (It does not contain an O-O bond.) According to the above method for producing phenol resin, the elastic modulus is reduced by having a flexible aliphatic hydrocarbon structure in the polymerization unit, resulting in low elasticity, and thus a phenol resin with excellent low elasticity can be obtained. Furthermore, the obtained phenol resin has multiple naphthylene ether structures and therefore has high heat resistance.

[0080] The dihydroxynaphthalene and the compound represented by general formula (3) used in the method for producing the phenolic resin of this embodiment are the same as the dihydroxynaphthalene and the compound represented by general formula (3) used in the reaction raw materials for the naphthylene ether resin of this embodiment, and the explanation of the dihydroxynaphthalene and the compound represented by general formula (3) in the naphthylene ether resin of this embodiment will be used by reference. Furthermore, the explanation of the phenolic resin obtained by the above method for producing the phenolic resin will also be used by reference to the explanation of the phenolic resin obtained in step (1) in the section (Method for producing naphthylene ether resin) above.

[0081] <Resin Composition> The resin composition of this embodiment contains the naphthylene ether resin of this embodiment. Because the resin composition contains the naphthylene ether resin of this embodiment, it can provide low dielectric properties and low elastic properties, and when the resin composition is cured, it can become a cured product with excellent low dielectric properties and low elastic properties.

[0082] In the resin composition of this embodiment, the content of the naphthylene ether resin of this embodiment is not limited, but is preferably 5% by mass or more and 80% by mass or less, and more preferably 5% by mass or more and 70% by mass or less, relative to the entire resin composition.

[0083] The resin composition of this embodiment preferably further contains a maleimide resin in addition to the naphthylene ether resin of this embodiment. This can improve heat resistance.

[0084] In the resin composition of this embodiment, the maleimide resin is not particularly limited, and known maleimide resins can be used. However, from the viewpoint of heat resistance, bismaleimide compounds containing two or more maleimide groups are preferred. Examples include 4,4'-diphenylmethanebismaleimide, m-phenylenebismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenylsulfone bismaleimide, 1,3-bis(3-maleimoidphenoxy)benzene, and 1,3-bis(4-maleimoidphenoxy)benzene.

[0085] From the viewpoint of dielectric properties, maleimide compounds containing an indane skeleton can also be preferably used as maleimide resins. Examples of such compounds include the maleimide described in International Publication No. 2020 / 217679. The maleimide resin is not limited, but for example, a maleimide resin having an indane skeleton represented by the following general formula (5) can be used. In formula (5), R a’ Each of these independently represents an alkyl group, alkyloxy group, or alkylthio group having 1 to 10 carbon atoms, an aryl group, aryloxy group, or arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a nitro group, a hydroxyl group, or a mercapto group, and k' represents an integer value from 0 to 4. When k' is 2 to 4, R a’ R may be the same or different within the same ring. ｂ’ Each of these independently represents an alkyl group, alkyloxy group, or alkylthio group having 1 to 10 carbon atoms, an aryl group, aryloxy group, or arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group, or a mercapto group, and l' represents an integer value from 0 to 3. When l' is 2 to 3, R ｂ’These may be the same or different within the same ring. n' is the average number of repeating units and represents a value between 0.95 and 10.0. Note that if l' and k' are 0, R a’ and R ｂ’ These each refer to a hydrogen atom.

[0086] The maleimide described in Japanese Patent Publication No. 2023-59784 can also be preferably used as a maleimide resin. Specifically, a maleimide resin represented by the following general formula (6) can be mentioned. In equation (6), there are multiple X ６１ , R ６１ , p ６１ Each exists independently, X ６１ R represents one of the structures represented by the following formulas (6-a) to (6-f). ６１ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aromatic group having 1 to 20 carbon atoms which may have substituents, p ６１ n represents a real number between 1 and 3. ６１ n is the number of repetitions, and its average value is 1 < n ６１ < 10 In formulas (6-a) to (6-f), * represents a bond to the benzene ring. There are multiple R ６２ , m ６１ , q ６１ , and r ６１ Each exists independently, R ６２ m represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aromatic group having 1 to 20 carbon atoms which may have substituents. ６１ is 1 to 50, q ６１ 1-4, r ６１ The 'x' represents a real number between 1 and 3.

[0087] The maleimide described in Japanese Patent Publication No. 2023-7239 can also be preferably used as a maleimide resin. Specifically, a maleimide resin represented by the following general formula (7) can be mentioned. In formula (7), R ７１ Each of these independently represents an alkyl group, and R ７２Each of these independently represents an alkyl group, alkoxy group, or alkylthio group having 1 to 10 carbon atoms; an aryl group, aryloxy group, or arylthio group having 6 to 10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; a hydroxyl group; or a mercapto group. ７３ , R ７４ , R ７５ and R ７６ Each of these independently represents a hydrogen atom or a methyl group, and R ７３ and R ７４ One side is a hydrogen atom, and the other side is a methyl group, R ７５ and R ７６ One side is a hydrogen atom, and the other side is a methyl group, X ７１ This is the following general formula (8): In formula (8), R ８７ and R ８８ Each of these independently represents a hydrogen atom or a methyl group, and R ８７ and R ８８ One side is a hydrogen atom, and the other side is a methyl group, R ８９ Each of these independently represents an alkyl group, alkoxy group, or alkylthio group having 1 to 10 carbon atoms; an aryl group, aryloxy group, or arylthio group having 6 to 10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; a hydroxyl group; or a mercapto group, t ８１ represents an integer from 0 to 4. ) represents a substituent represented by r ７１ is, X ７１ X per benzene ring to which is bonded ７１ This is the average number of substitutions, representing a number between 0 and 4, p ７１ represents an integer from 1 to 3, and q ７１ k represents an integer from 0 to 4, and ７１ This represents an integer between 1 and 100.

[0088] Furthermore, it is also possible to use one or more other maleimide resins in combination, and the method is not particularly limited.

[0089] The maleimide resin may be used alone, or it may be used in combination with maleimide resins having different weight-average molecular weights, or with the maleimide resin and its prepolymer.

[0090] The number-average molecular weight (Mn) of the maleimide resin is preferably in the range of 200 to 1500, and more preferably in the range of 300 to 1500. The weight-average molecular weight (Mw) of the polymaleimide resin is preferably in the range of 280 to 2000, and more preferably in the range of 330 to 2000.

[0091] The resin compositions of this disclosure may contain organic peroxides and radical polymerization initiators, curing accelerators, and / or curing agents such as azo compounds, and may further contain various compounding agents such as silane coupling agents, mold release agents, pigments, emulsifiers, halogenated and non-halogenated flame retardants, and inorganic fillers such as silica, as needed. In addition, other resins such as epoxy resins, phenolic resins, activated ester resins, cyanate resins, styrene-butadiene resins, triallyl isocyanurate, and terminally modified polyphenylene ether resins may be appropriately blended in addition to the naphthylene ether resin and the polymaleimide resin of this embodiment, as long as the purpose of this disclosure is not impaired.

[0092] The content of the curing agent in the resin composition is not limited, but can be, for example, 0.1% by mass or more and 10% by mass or less. The content of various compounding agents can be, for example, 1% by mass or more and 80% by mass or less. The content of other resins can be, for example, 1% by mass or more and 50% by mass or less.

[0093] The resin composition of this embodiment can be produced by mixing the naphthylene ether resin of this embodiment with, optionally, maleimide resin, various compounding agents, and other resins, using known methods.

[0094] <Cured Product> The cured product of this embodiment is a cured product of the resin composition of this embodiment. That is, the cured product of this embodiment can be obtained by curing the resin composition of this embodiment. The cured product can be easily cured by a method similar to that of conventionally known methods. Examples of the cured product include molded cured products such as laminates, cast products, adhesive layers, coatings, and films. Because the cured product of this embodiment contains the naphthylene ether resin of this embodiment, it has excellent low dielectric properties and low elastic properties.

[0095] From the viewpoint of low dielectric properties, the cured product of this embodiment preferably has a dielectric constant at 10 GHz of 3.6 or less, 3.2 or less, or 3.0 or less, and more preferably 2.8 or less. Furthermore, the cured product of this embodiment preferably has a dielectric constant at 10 GHz after moisture absorption of 3.6 or less, 3.2 or less, or 3.0 or less, and more preferably 2.8 or less.

[0096] From the viewpoint of low dielectric properties, the cured product of this embodiment preferably has a dielectric loss tangent at 10 GHz of 0.012 or less, more preferably 0.008 or less, and even more preferably 0.005 or less. Furthermore, the cured product of this embodiment preferably has a dielectric loss tangent at 10 GHz after moisture absorption of 0.012 or less, 0.010 or less, 0.009 or less, 0.008 or less, and 0.007 or less. The dielectric constant and dielectric loss tangent can be measured in accordance with JIS-C-6481.

[0097] The cured product of this embodiment preferably has an elastic modulus of 3.5 GPa or less. A low elastic modulus of the cured product is preferable because it can reduce stress caused by curing shrinkage and thermal expansion / contraction due to the refrigeration cycle, thereby suppressing deformation of articles such as substrates to which the cured product is applied. From a similar viewpoint, the elastic modulus of the cured product is preferably 3.3 GPa or less, more preferably 3.0 GPa or less, even more preferably 2.5 GPa or less, still preferably 2.0 GPa or less, and particularly preferably 1.8 GPa or less. The elastic modulus of the cured product may also be 1.0 GPa or more.

[0098] From the viewpoint of heat resistance, the cured product of this embodiment preferably has a glass transition temperature of 120°C or higher, and more preferably 140°C or higher. The glass transition temperature can be measured using a viscoelasticity measuring device, and specifically, it can be measured by the method of the examples described later.

[0099] <Prepreg> This disclosure also relates to a prepreg having a reinforcing substrate and a semi-cured resin composition of this embodiment impregnated into the reinforcing substrate. A method for obtaining a prepreg from the above resin composition is to impregnate a reinforcing substrate (paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, glass roving cloth, etc.) with a varnished resin composition made by blending it with an organic solvent, as described later, and then heat it at a heating temperature corresponding to the type of solvent used, preferably 50 to 170°C, to semi-cur (or uncured) the resin composition and obtain a prepreg. The mass ratio of the resin composition to the reinforcing substrate used at this time is not particularly limited, but it is usually preferable to prepare the prepreg so that the resin content is 20 to 60% by mass. In this embodiment, the semi-cured resin composition can be obtained by adjusting the heating temperature and heating time to stop the curing reaction midway without completing it. For example, the semi-cured product may have a degree of curing of 85% or less and 5% or more. On the other hand, the cured product in this embodiment may have a higher degree of curing than the semi-cured product. The degree of curing of the semi-cured product can be calculated by measuring the heat generated during curing of the resin composition and the heat generated during curing of the semi-cured product using DSC, and using the following formula: Degree of curing (%) = [1 - (Heat generated during curing of semi-cured product / Heat generated during curing of resin composition)] × 100

[0100] Examples of organic solvents used in the production of prepregs include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, and propylene glycol monomethyl ether acetate. The selection and appropriate amount of these solvents can be appropriately chosen depending on the application. For example, when further manufacturing printed circuit boards from prepregs as described below, it is preferable to use polar solvents with a boiling point of 160°C or lower, such as methyl ethyl ketone, acetone, and dimethylformamide, and it is also preferable to use them in a proportion that results in a non-volatile content of 40 to 80% by mass.

[0101] <Circuit Boards> This disclosure also relates to circuit boards which are laminates of the prepreg and copper foil. A method for obtaining a printed circuit board from the resin composition of this embodiment is to laminate the prepreg by a conventional method, add copper foil as appropriate, and heat-press them together at 170 to 300°C for 10 minutes to 3 hours under pressure of 1 to 10 MPa.

[0102] <Build-up Film> This disclosure also relates to a build-up film containing the resin composition of this embodiment. A method for manufacturing the build-up film of this embodiment is to apply the resin composition onto a support film to form a resin composition layer and thereby produce an adhesive film for a multilayer printed circuit board.

[0103] When manufacturing a build-up film from a resin composition, it is essential that the film softens under the lamination temperature conditions (usually 70 to 140°C) in the vacuum lamination method and exhibits fluidity (resin flow) that allows for simultaneous lamination of the circuit board and resin filling of via holes or through holes present in the circuit board. It is preferable to formulate the above-mentioned components in such a way as to exhibit these characteristics.

[0104] Here, the diameter of the through-holes in a multilayer printed circuit board is typically 0.1 to 0.5 mm, and the depth is typically 0.1 to 1.2 mm. It is generally preferable to be able to fill the holes with resin within this range. When laminating both sides of the circuit board, it is desirable to fill about half of the through-holes.

[0105] The adhesive film described above can be manufactured by first preparing a varnish-like resin composition, then applying this varnish-like composition to the surface of a support film, and finally drying the organic solvent by heating or blowing hot air to form a composition layer made of the resin composition.

[0106] The thickness of the formed composition layer is usually preferably greater than or equal to the thickness of the conductor layer. Since the thickness of the conductor layer of a circuit board is usually in the range of 5 to 70 μm, the thickness of the resin composition layer is preferably 10 to 100 μm.

[0107] Furthermore, the composition layer in this embodiment may be protected by a protective film, which will be described later. Protecting it with a protective film can prevent dirt and other debris from adhering to the surface of the resin composition layer and prevent scratches.

[0108] The support film and protective film mentioned above can be made of polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate, polycarbonate, polyimide, and also release paper and metal foils such as copper foil and aluminum foil. In addition, the support film and protective film may be treated with a mat treatment, corona treatment, or release treatment.

[0109] The thickness of the support film is not particularly limited, but is usually 10 to 150 μm, and preferably in the range of 25 to 50 μm. The thickness of the protective film is preferably 1 to 40 μm.

[0110] The support film described above is peeled off after lamination to the circuit board or after an insulating layer has been formed by heat curing. Peeling off the support film after heat curing the adhesive film prevents the adhesion of dust and other contaminants during the curing process. When peeling off after curing, the support film is usually treated with a release agent beforehand.

[0111] <Semiconductor Encapsulating Material> This disclosure also relates to a semiconductor encapsulating material containing the resin composition of this embodiment. The semiconductor encapsulating material obtained using the resin composition of this embodiment is a preferred embodiment because, by using the above-mentioned resin composition of this disclosure, it is possible to expect suppression of warping of molded products and improvement of transmission characteristics. The resin composition of this embodiment used in the semiconductor encapsulating material may contain an inorganic filler. The filling ratio of the inorganic filler can be, for example, 0.5 to 1200 parts by mass of the inorganic filler per 100 parts by mass of the resin composition of this embodiment. Examples of the inorganic filler include barium sulfate, barium titanate, amorphous silica, crystalline silica, Neuburg silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, silicon nitride, and aluminum nitride.

[0112] A method for obtaining the aforementioned semiconductor encapsulating material includes, as necessary, a method of thoroughly melting and mixing the resin composition of this embodiment with an optional additive until uniform, using an extruder, kneader, or roll.

[0113] <Semiconductor Device> This disclosure also relates to a semiconductor device including a cured product of the semiconductor encapsulation material. A semiconductor device obtained using the semiconductor encapsulation material obtained using the resin composition of this embodiment uses the naphthylene ether resin of this disclosure and therefore exhibits excellent low dielectric properties and low elastic properties.

[0114] A method for obtaining the semiconductor device involves forming the semiconductor encapsulating material using a casting, transfer molding machine, or injection molding machine, and then heat-curing it in a temperature range of room temperature (20°C) to 250°C.

[0115] The present invention will be described in more detail below with reference to examples, but the present invention is not limited in any way to the following examples.

[0116] <Measurement Method> (1) Measurement of Dielectric Properties (Dielectric Constant and Dielectric Loss Tangent) For the cured material obtained by the method described below, the dielectric constant (Dk) and dielectric loss tangent (Df) at 10 GHz were measured in accordance with JIS-C-6481 using an impedance material analyzer "HP4291B" manufactured by Agilent Technologies, Inc., after being completely dried and stored in a room at 23°C and 50% humidity for 24 hours.

[0117] (2) Measurement of elastic modulus The flexural modulus of the test specimen was measured in accordance with JIS-K6911 for the hardened material obtained by the method described below.

[0118] (3) Measurement of Glass Transition Temperature As an evaluation of heat resistance, the glass transition temperature was measured. The hardened material obtained by the method described later was cut into pieces with a thickness of 1.8 mm, a width of 5 mm, and a length of 54 mm, and these were used as test specimens. The dynamic viscoelasticity of these test specimens was measured using the following apparatus and conditions, and the heat resistance was evaluated by the glass transition temperature. Measurement apparatus: Rheometric Solid Viscoelasticity Measurement Device "RSAII" Rectangular Tension Method: Frequency 1 Hz, heating rate 3°C / min

[0119] (4) Measurement of hydroxyl group equivalents The hydroxyl group equivalents were measured by a method in accordance with the neutralization titration method specified in JIS K0070 (1992).

[0120] (5) Measurement of Amine Equivalents The amine equivalents were measured by the following method. Approximately 2.5 g of each of the above intermediate amine compounds, 7.5 g of pyridine, 2.5 g of acetic anhydride, and 7.5 g of triphenylphosphine were accurately weighed into a 500 mL stoppered Erlenmeyer flask. A condenser was attached, and the mixture was heated under reflux in an oil bath set to 120°C for 150 minutes. After cooling, 5.0 mL of distilled water, 100 mL of propylene glycol monomethyl ether, and 75 mL of tetrahydrofuran were added, and the mixture was titrated by potentiometric titration with a 0.5 mol / L potassium hydroxide-ethanol solution. A blank test was performed in the same manner to correct the result. Amine equivalent (g / equivalent) = (S × 2,000) / (Blank - A) S: Amount of sample (g) A: Amount of 0.5 mol / L potassium hydroxide-ethanol solution consumed (mL) Blank: Amount of 0.5 mol / L potassium hydroxide-ethanol solution consumed in the blank test (mL)

[0121] (6) GPC measurement The number-average molecular weight (Mn), weight-average molecular weight (Mw), and molecular weight distribution (Mw / Mn) were calculated using the following measuring devices and conditions. "Measuring device" Tosoh Corporation "HLC-8320 GPC" "Measurement conditions" Column: Tosoh Corporation Guard column "HXL-L" + Tosoh Corporation "TSK-GEL G2000HXL" + Tosoh Corporation "TSK-GEL G2000HXL" + Tosoh Corporation "TSK-GEL G3000HXL" + Tosoh Corporation "TSK-GEL G4000HXL" Detector: RI (differential refractometer) Data processing: Tosoh Corporation "GPC workstation EcoSEC-WorkStation" Measurement conditions: Column temperature 40℃ Developing solvent tetrahydrofuran flow rate 1.0 ml / min Standard: In accordance with the measurement manual for the "GPC workstation EcoSEC-WorkStation" mentioned above, the following monodisperse polystyrene with known molecular weight was used. (Polystyrene used) Tosoh Corporation "A-500" Tosoh Corporation "A-1000" Tosoh Corporation "A-2500" Tosoh Corporation "A-5000" Tosoh Corporation "F-1" Tosoh Corporation "F-2" Tosoh Corporation "F-4" Tosoh Corporation "F-10" Tosoh Corporation "F-20" Tosoh Corporation "F-40" Tosoh Corporation "F-80" Tosoh Corporation "F-128" Sample: A tetrahydrofuran solution of maleimide resin obtained in the synthesis example, at a concentration of 1.0% by mass in terms of resin solids, filtered through a microfilter (50 μl).

[0122] (7) Measurement of softening point The softening point was measured in accordance with JIS K7234.

[0123] (8) FD-MS Spectrum Measurement The FD-MS spectrum was measured using the following measuring device and conditions. Measuring device: JMS-T100GC AccuTOF Measuring conditions Measurement range: m / z = 4.00 to 2000.00 Rate of change: 51.2 mA / min Final current value: 45 mA Cathode voltage: -10 kV Recording interval: 0.07 sec

[0124] (7) １３ The resin obtained in the C-NMR measurement example １３ The C-NMR spectrum was measured using the following measuring equipment and conditions. １３ C-NMR: JEOL RESONANCE "JNM-ECZ400S" Resonance frequency: 100 MHz Number of integration cycles: 4000 Solvent: Chloroform-d Sample concentration: 12% by mass Relaxation reagent: Chromium(III) acetylacetonate

[0125] <Synthesis Method> The resins used in the examples and comparative examples were synthesized according to the following synthesis examples.

[0126] (Synthesis Example 1: Synthesis of Phenolic Resin (A-1)) 300 g (1.88 mol) of 2,7-dihydroxynaphthalene, 203 g (1.88 mol) of benzyl alcohol, 150 g (0.94 mol) of 1,9-nonanediol, 300 g of xylene, and 6.5 g of p-toluenesulfonic acid were charged into a 2 L flask equipped with a thermometer, condenser, Dean-Stark trap, and stirrer, and heated while stirring. The condensation water produced by the reaction was removed using a Dean-Stark tube while the temperature was increased, and the reaction was carried out under reflux at 150-160°C for 9 hours. After cooling to 60°C, the mixture was diluted with 900 g of xylene, and then neutralized with a 5% sodium hydroxide aqueous solution until neutral. Subsequently, the catalyst salt was removed by three separatory washes with water. The mixture was heated to 190°C, and the low molecular weight products were removed by distillation under reduced pressure to obtain phenolic resin (A-1) represented by the following formula. The obtained phenolic resin (A-1) １３ The 1C-NMR spectrum is shown in Figure 1, the GPC chart in Figure 2, and the FD-MS spectrum in Figure 3. The hydroxyl group equivalent was 360 g / equivalent. １３The formation of the following structure was confirmed from the C-NMR spectrum and mass spectrum.

[0127] (Synthesis Example 2: Synthesis of Phenolic Resin (A-2)) The experimental procedure was carried out in the same manner as in Synthesis Example 1, except that the amount of 1,9-nonanediol used was changed to 210 g (1.31 mol), and phenolic resin (A-2) represented by the following formula was obtained. The GPC chart of the obtained phenolic resin (A-2) is shown in Figure 4. The hydroxyl group equivalent was 590 g / equivalent.

[0128] (Synthesis Example 3: Synthesis of Phenolic Resin (A-3)) The experimental procedure was carried out in the same manner as in Synthesis Example 1, except that 1,9-nonanediol was replaced with 378 g of pripol2033 (manufactured by Croda, 36 carbon atoms, hydroxyl group equivalent 270 g / equivalent), and phenolic resin (A-3) represented by the following formula was obtained. The GPC chart of the obtained phenolic resin (A-3) is shown in Figure 5. The hydroxyl group equivalent was 1133 g / equivalent.

[0129] (Synthesis Example 4: Synthesis of Phenolic Resin (A-4)) The experimental procedure was carried out in the same manner as in Synthesis Example 2, except that 2,7-dihydroxynaphthalene was replaced with 1,5-dihydroxynaphthalene, and phenolic resin (A-4) represented by the following formula was obtained. The GPC chart of the obtained phenolic resin (A-4) is shown in Figure 6. The hydroxyl group equivalent was 513 g / equivalent.

[0130] (Synthesis Example 5: Synthesis of Phenolic Resin (A-5)) The experimental procedure was carried out in the same manner as in Synthesis Example 3, except that 2,7-dihydroxynaphthalene was replaced with 1,5-dihydroxynaphthalene and the amount of p-toluenesulfonic acid added was changed to 12.9 g, and phenolic resin (A-5) represented by the following formula was obtained. The GPC chart of the obtained phenolic resin (A-5) is shown in Figure 7. The hydroxyl group equivalent was 882 g / equivalent.

[0131] (Example 1: Synthesis of naphthylene ether resin (B-1) having a methacryloyl group at the end, using phenolic resin (A-1)) 250 g (0.694 equivalents) of phenolic resin (A-1) and 500 g of toluene were added to a four-necked flask equipped with a stirrer, thermometer, dropping funnel, and condenser, and stirred until dissolved. The temperature was raised to approximately 85°C, and 4.22 g (0.0345 mol) of dimethylaminopyridine and 92.7 g (0.916 mol) of triethylamine were added. After all the solids had dissolved, 79.7 g (0.763 mol) of methacrylate chloride was gradually added. The resulting solution was maintained at 85°C for 20 hours while being mixed. The reaction product was washed with water to remove the by-product triethylamine hydrochloride and excess raw materials. Naphthylene ether resin (B-1), represented by the following formula, was obtained by dehydration and desolventing under heating and reduced pressure. The GPC chart for the obtained naphthylene ether resin (B-1) is shown in Figure 8.

[0132] (Example 2: Synthesis of naphthylene ether resin (B-2) having methacryloyl groups at the terminals using phenol resin (A-2)) The experimental procedure was carried out in the same manner as in Synthesis Example 6, except that phenol resin (A-1) was replaced with 410 g of phenol resin (A-2) and toluene was replaced with 820 g to obtain naphthylene ether resin (B-2) represented by the following formula. The GPC chart of the obtained naphthylene ether resin (B-2) is shown in Figure 9.

[0133] (Example 3: Synthesis of naphthylene ether resin (B-3) having vinylphenyl groups at the ends using phenolic resin (A-3)) 250 g of (A-3), 142 g of isopropanol, 332 g of toluene, 37 g of chloromethylstyrene (product name CMS-P, manufactured by AGC Seimi Chemical Co., Ltd.), and 1.4 g of tetrabutylammonium bromide were charged into a flask equipped with a stirrer, a Dean-Stark apparatus, and a condenser. The mixture was heated to 75°C while stirring and dissolved. 59 g of 49% sodium hydroxide aqueous solution was added dropwise over 30 minutes, and the reaction was continued for 5 hours. After removing the catalyst residue from the reaction solution by washing with water, the volatile components were adjusted by heating and reduced pressure to obtain naphthylene ether resin (B-3) represented by the following formula. The GPC chart of the obtained naphthylene ether resin (B-3) is shown in Figure 10.

[0134] (Example 4: Synthesis of naphthylene ether resin (B-4) having methacryloyl groups at the ends using phenol resin (A-4)) The experimental procedure was carried out in the same manner as in Synthesis Example 6, except that phenol resin (A-1) was replaced with 356 g of phenol resin (A-4) and 712 g of toluene, and a naphthylene ether resin (B-4) represented by the following formula was obtained. The GPC chart of the obtained naphthylene ether resin (B-4) is shown in Figure 11.

[0135] (Example 5: Synthesis of Naphthylene Ether Resin (B-5) Having Vinylphenyl Groups at the End Using Phenolic Resin (A-5)) 250 g of phenolic resin (A-5), 147 g of isopropanol, 344 g of toluene, 48 g of chloromethylstyrene (product name CMS-P, manufactured by AGC Seimi Chemical Co., Ltd.), and 1.5 g of tetrabutylammonium bromide were charged into a flask equipped with a stirrer, a Dean-Stark apparatus, and a condenser. The mixture was heated to 75°C while stirring and dissolved. 76 g of 49% sodium hydroxide aqueous solution was added dropwise over 30 minutes, and the reaction was continued for 5 hours. After removing the catalyst residue from the reaction solution by washing with water, the volatile components were adjusted by heating and reduced pressure to obtain naphthylene ether resin (B-5) represented by the following formula. The GPC chart of the obtained naphthylene ether resin (B-5) is shown in Figure 12.

[0136] (Synthesis Example 6: Synthesis of a naphthylene ether resin (C-1) having a methacryloyl group at the terminal and lacking an aliphatic hydrocarbon structure) The phenol resin (A-1) in Synthesis Example 6 was replaced with an aralkyl group-containing naphthylene ether resin (hydroxyl group equivalent 156 g / eq, softening point 83°C) synthesized in the same manner as in Example 7 of Japanese Patent Application Publication No. 2006-307162. The experimental procedure was carried out in the same manner except that 108 g of the aralkyl group-containing naphthylene ether resin and 216 g of toluene were changed to obtain a naphthylene ether resin (C-1) that lacks an aliphatic hydrocarbon structure, represented by the following formula.

[0137] (Synthesis Example 7: Synthesis of Naphthylene Ether Resin (C-2) Having Vinylphenyl Groups at the Terminals and Not Having an Aliphatic Hydrocarbon Structure) 250 g of aralkyl group-containing naphthylene ether resin (hydroxyl group equivalent 156 g / eq, softening point 83°C), synthesized in the same manner as in Example 7 of JP 2006-307162, 147 g of isopropanol, 344 g of toluene, 140 g of chloromethylstyrene (product name CMS-P, manufactured by AGC Seimi Chemical Co., Ltd.), and 1.5 g of tetrabutylammonium bromide were charged into a flask equipped with a stirrer, a Dean-Stark apparatus, and a condenser. The mixture was heated to 75°C while stirring and dissolved. 224 g of 49% sodium hydroxide aqueous solution was added dropwise over 30 minutes, and the reaction was continued for 5 hours. After removing catalyst residue from the reaction solution by washing with water, the volatile components were adjusted by heating and reduced pressure to obtain a naphthylene ether resin (C-2) that does not have an aliphatic hydrocarbon structure represented by the following formula.

[0138] (Synthesis Example 8: Synthesis of Polyindane-type Maleimide Resin) 48.5 g (0.4 mol) of 2,6-dimethylaniline, 272.0 g (1.4 mol) of α,α'-dihydroxy-1,3-diisopropylbenzene, 280 g of xylene, and 70 g of activated clay were charged into a 1 L flask equipped with a thermometer, condenser, Dean-Stark trap, and stirrer, and heated to 120°C while stirring. The temperature was further increased to 210°C while removing the distillate using a Dean-Stark tube, and the reaction was carried out for 3 hours. After that, the mixture was cooled to 140°C, 145.4 g (1.2 mol) of 2,6-dimethylaniline was charged, and the temperature was increased to 220°C, and the reaction was carried out for 3 hours. After the reaction, the mixture was air-cooled to 100°C, diluted with 300 g of toluene, the activated clay was removed by filtration, and 364.1 g of the intermediate amine compound was obtained by distilling off the solvent and unreacted low molecular weight substances under reduced pressure. The amine equivalent was 298, and the softening point was 70°C. 131.8 g (1.3 mol) of maleic anhydride and 700 g of toluene were placed in a 2 L flask equipped with a thermometer, condenser, Dean-Stark trap, and stirrer, and stirred at room temperature. Next, a mixed solution of 364.1 g of the intermediate amine compound and 175 g of DMF was added dropwise over 1 hour. After the addition was complete, the reaction was allowed to continue at room temperature for another 2 hours. 37.1 g of p-toluenesulfonic acid monohydrate was added, the reaction mixture was heated, and the azeotropic water and toluene were cooled and separated under reflux. Only the toluene was returned to the system, and the dehydration reaction was carried out for 8 hours. After air cooling to room temperature, the brown solution was concentrated under reduced pressure and dissolved in 600 g of ethyl acetate. The mixture was washed three times with 150 g of deionized water and three times with 150 g of 2% sodium bicarbonate aqueous solution. Sodium sulfate was added, the mixture was dried, and the reaction product was concentrated under reduced pressure. The resulting product was vacuum-dried at 80°C for 4 hours to obtain 413.0 g of a product containing polyindan-type maleimide resin. The FD-MS spectrum (not shown) of this polyindan-type maleimide resin showed peaks at M+ = 560, 718, and 876, with each peak corresponding to n = 0, 1, and 2, respectively. The value of the number of repeating units n in the indan skeleton of the polyindan-type maleimide resin (based on the number-average molecular weight) was determined by GPC (not shown) to be n = 1.47, and the molecular weight distribution (Mw / Mn) = 1.81.

[0139] <Examples 6-10 and Comparative Examples 1-3> The resins obtained according to the above synthesis examples were blended in the proportions shown in Table 1 to prepare the various resin compositions of the examples and comparative examples. Then, 0.5% by weight of perbutyl P (manufactured by NOF Corporation) was added to each resin composition as a curing catalyst, heated and mixed, and then poured into a mold processed to a thickness of 2 mm. A cured product was produced by heating at 170°C for 30 minutes and then at 200°C for 2 hours. The obtained cured products were evaluated using the measurement method described above. The blending and evaluation results are shown in Table 1.

[0140]

[0141] Table 1 shows that the cured product using the naphthylene ether resin of this embodiment exhibits excellent low dielectric properties and low elastic properties. Furthermore, it can be seen that the naphthylene ether resin of this embodiment and the resin composition containing said naphthylene ether resin can produce cured products with excellent low dielectric properties and low elastic properties. Additionally, the cured product using the naphthylene ether resin of this embodiment also exhibits excellent low dielectric properties after moisture absorption.

[0142] This application asserts the interests of Japanese Patent Application No. 2024-173888, filed on October 2, 2024, and the contents of the aforementioned application are incorporated herein by reference.

[0143] According to this disclosure, it is possible to provide a naphthylene ether resin capable of producing a cured product with excellent low dielectric properties and low elastic properties, a resin composition containing the naphthylene ether resin, and a cured product with excellent low dielectric properties and low elastic properties.

Claims

1. A naphthylene ether resin represented by the following general formula (1). (In general formula (1), R １１ａ and R １１ｂ each independently represent a radically polymerizable unsaturated group, L １１ and L １３ each independently represent a single bond or a divalent aliphatic hydrocarbon group, and one or more —CH ２ — of the aliphatic hydrocarbon group may be substituted with —CH(—OH)—, —O—, —C(═O)— or an arylene group which may have a substituent, L １２ represents a divalent aliphatic hydrocarbon group, and one or more —CH ２ — of the aliphatic hydrocarbon group may be substituted with —CH(—OH)—, —O—, —C(═O)— or an arylene group which may have a substituent, R １２ and R １４ each independently represent an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms, R １３ and R １５ each independently represent a hydroxyl group, a halogen atom, an alkoxy group, an alkyl group, an alkenyl group, or an aryl group, a and c are each independently an integer of 0 to 6, b and d are each independently an integer of 0 to 6, provided that the sum of a + b is at most 6 and the sum of c + d is at most 6, n is 1 to 20, provided that the molecule does not contain an —O—O— bond.) 2. L in the general formula (1) １２ The naphthylene ether resin according to claim 1, wherein each independently represents an alicyclic hydrocarbon group or a divalent aliphatic hydrocarbon group represented by the following general formula (2). (In general formula (2), L ２１ and L ２２ Each of the above independently represents a divalent aliphatic hydrocarbon group, and A represents a single bond or a divalent aliphatic hydrocarbon group, provided that the divalent aliphatic hydrocarbon group contains one or more -CH ２ The - may be substituted with -CH(-OH)-, -O-, -C(=O)-, or an arylene group which may have a substituent, and * represents a bond, where A does not contain an -O-O- bond.

3. R ​​in the general formula (1) １１ａ and R １１ｂ The naphthylene ether resin according to claim 1, wherein each of the groups is independently selected from the group consisting of an acryloyl group, a methacryloyl group, and a vinylphenyl group.

4. L in the general formula (1) １２ The naphthylene ether resin according to claim 1, wherein the number of carbon atoms is 7 or more.

5. L in the general formula (1) １２ The naphthylene ether resin according to claim 1, wherein the molecular weight per molecule is 98 or more.

6. The naphthylene ether resin according to claim 1, wherein dihydroxynaphthalene, a compound represented by the following general formula (3), and a compound having a radically polymerizable unsaturated group are used as reaction raw materials (I). (In general formula (3), L １２ represents a divalent aliphatic hydrocarbon group, and one or more -CH groups are present in the aliphatic hydrocarbon group. ２ - may be substituted with -CH(-OH)-, -O-, -C(=O)- or an arylene group which may have substituents, however L １２ (It does not contain an O-O bond.) 7. A resin composition comprising the naphthylene ether resin according to any one of claims 1 to 6.

8. The resin composition according to claim 7, further comprising a maleimide resin.

9. A cured product of the resin composition according to claim 7.

10. A prepreg having a reinforcing substrate and a semi-cured product of the resin composition according to claim 7 impregnated into the reinforcing substrate.

11. A circuit board which is a laminate of the prepreg and copper foil according to claim 10.

12. A build-up film containing the resin composition described in claim 7.

13. A semiconductor encapsulant containing the resin composition described in claim 7.

14. A semiconductor device comprising a cured product of the semiconductor encapsulant described in claim 13.

15. A method for producing a phenol resin, comprising reacting dihydroxynaphthalene with a compound represented by the following general formula (3). (In general formula (3), L １２ represents a divalent aliphatic hydrocarbon group, and one or more -CH groups are present in the aliphatic hydrocarbon group. ２ - may be substituted with -CH(-OH)-, -O-, -C(=O)- or an arylene group which may have substituents, however L １２ (It does not contain an O-O bond.) 16. A method for producing a naphthylene ether resin, comprising: (1) a step of reacting the dihydroxynaphthalene with a compound represented by the general formula (3) to obtain the phenol resin described in claim 15; and (2) a step of reacting the phenol resin with a compound having a radically polymerizable unsaturated group to obtain a naphthylene ether resin.

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