Polyether compound, resin composition, cured product, build-up film, copper-clad laminate, laminate, electric / electronic component, use of resin composition as raw material for electric / electronic component, and method for producing polyether compound

Abstract

Provided is a polyether compound which has excellent solvent solubility and can provide a cured product excellent in low dielectric characteristics and metal adhesion in a higher frequency environment. A polyether compound according to the present invention is represented by formula (1) below.

Description

Polyether compound, resin composition, cured product, build-up film, copper-clad laminate, laminate, electric / electronic component, use of resin composition as raw material for electric / electronic component, and method for producing polyether compound

[0001] The present invention relates to a polyether compound, a resin composition, a cured product, a build-up film, a copper-clad laminate, a laminate, an electric / electronic component, use of the resin composition as a raw material for the electric / electronic component, and a method for producing the polyether compound. This application claims priority based on Japanese Patent Application No. 2024-048509, filed on March 25, 2024, the contents of which are incorporated herein by reference.

[0002] In recent years, the multilayer circuit boards used in electric and electronic devices have become smaller, lighter, and more functional, and as a result, there is a demand for further multilayering, higher density, thinner thickness, lighter weight, and improved reliability and moldability.

[0003] Curable resins used as materials for electrical and electronic components, such as laminates for electrical and electronic circuits, are required to have a wide range of performance characteristics. One of the most important characteristics is low dielectric properties. In recent years, communication frequencies have become higher to improve the amount and speed of information transmission. In this context, increased transmission loss (α) has become a major issue. The lower the α value, the less attenuation of the information signal, ensuring high communication reliability. One way to reduce α is to reduce dielectric loss, one of its components. Because dielectric loss is proportional to frequency, communication in the high-frequency range experiences greater loss, leading to reduced reliability. However, by reducing the dielectric loss tangent (tan δ), which is also proportional to frequency, dielectric loss and α can be reduced. Therefore, for high-speed transmission of communication signals, materials with low dielectric loss tangent (tan δ), i.e., materials with low dielectric properties, are required.

[0004] Another way to reduce transmission loss (α) is to reduce scattering loss. As the frequency increases, the skin effect becomes greater, causing signals to scatter in the roughened areas near the conductor surface and be lost as heat. Therefore, reducing the roughness of the conductor surface is an effective way to reduce scattering loss. However, reducing the roughness of the conductor surface reduces adhesion with the thermosetting resin used as the material, resulting in reduced reliability. In other words, the thermosetting resin used as the material must have low dielectric properties as well as high adhesion to the metal used as the conductor.

[0005] Furthermore, when the curable resin composition is cured on an industrial scale and applied to electric or electronic parts, the material may be dissolved in a solvent to adjust the viscosity and used as a varnish, and therefore the material needs to have excellent solvent solubility.

[0006] Patent Document 1 proposes a polyether compound containing an ethylenically unsaturated double bond at the end of a reaction product of a bisphenol compound and paraxylene dichloride.

[0007] Patent Document 2 proposes a polyether compound containing an ethylenically unsaturated double bond at the end of a reaction product of a phenol compound having a diphenylphosphine oxide skeleton and metaxylene dichloride.

[0008] International Publication No. 2014 / 156778 Japanese Patent Application Laid-Open No. 2011-84697

[0009] A cured product using a curable resin composition containing the compound described in Patent Document 1 has excellent low dielectric properties at 2 GHz, but according to studies by the present inventors, it has been found that the cured product is insufficient in terms of low dielectric properties or metal adhesion in a higher frequency environment (10 GHz).

[0010] According to the investigations of the present inventors, it has been found that the curable resin composition containing the compound described in Patent Document 2 has insufficient solvent solubility.

[0011] The present invention has been made in view of the above problems, and an object of the present invention is to provide a polyether compound that has excellent solvent solubility and can give a cured product that has low dielectric properties and excellent metal adhesion in a higher frequency environment. Also, an object of the present invention is to provide a resin composition that has excellent solvent solubility and can give a cured product that has low dielectric properties and excellent metal adhesion in a higher frequency environment, a cured product that has low dielectric properties and excellent metal adhesion in a higher frequency environment, a laminate containing the cured product, an electric / electronic component that contains the cured product, and an electric / electronic component that contains the laminate.

[0012] As a result of extensive investigations aimed at solving the above-mentioned problems, the present inventors have found that a polyether compound having a specific structure can solve the above-mentioned problems, and have thus completed the present invention. That is, the gist of the present invention is as follows.

[0013] [1] A polyether compound represented by the following formula (1):

[0014]

[0015] In formula (1), l and n represent 0 or 1, m represents an integer of 1 to 50, and Ar １ each independently represents an aromatic hydrocarbon group having 6 to 100 carbon atoms and not having a structure represented by formula (2), Ar ２ represents a structure represented by formula (3) or a structure represented by formula (4) when m is 1 and n is 0, and when m is 2 to 50 or n is 1, each independently represents at least one structure selected from the group consisting of a structure represented by formula (3) and a structure represented by formula (4), and each Y independently represents a group containing an ethylenically unsaturated double bond and having 3 to 50 carbon atoms.

[0016]

[0017] In formulas (2) to (4), the symbol "*" represents a bond, and A １ ~A １０ are each independently any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group, and a naphthyl group, and R １ ~R ８are each independently any one selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms. [2] The polyether compound according to [1], wherein Y in the formula (1) contains at least one group selected from the group consisting of a 2-vinylbenzyl group, a 3-vinylbenzyl group, a 4-vinylbenzyl group, an allyl group, a methallyl group, a cinnamyl group, an acryloyl group, a methacryloyl group, a 2-allylphenyl group, a 2-propenylphenyl group, a 4-vinylphenyl group, a 4-isopropenylphenyl group, a 2-methoxy-4-allylphenyl group, and a 2-methoxy-4-propenylphenyl group. [3] The polyether compound according to [1], wherein Ar in the formula (1) １ is at least one group selected from the group consisting of groups represented by formulas (5) to (8).

[0018]

[0019] In formulas (5) to (8), the symbol "*" represents a bond, and X ４ represents a direct bond, a divalent hydrocarbon group having 1 to 20 carbon atoms, —O—, —S—, —CO—, —C(O)—O—, —C(O)—NH—, —SO—, or —SO ２ -, -C(CF ３ ) ２ - and -P(O)-, X5 is a trivalent hydrocarbon group having 1 to 20 carbon atoms, and X ６ is a tetravalent hydrocarbon group having 1 to 20 carbon atoms, and R ９ ~R ５０ are each independently any one selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms, and Z represents a structure represented by the following formula (9):

[0020]

[0021] In formula (9), the symbol "*" represents a bond, M represents an integer of 1 to 50, N represents 0 or 1, and Ar １ and Y is Ar in formula (1). １ and Y, and Ar ２represents a structure represented by formula (3) or a structure represented by formula (4) when M is 1 and N is 0, or when M is 0 and N is 1; and when M is 2 to 50, or when M is 1 and N is 1, each independently represents at least one structure selected from the group consisting of a structure represented by formula (3) and a structure represented by formula (4). [4] A polyether compound according to any one of [1] to [3], having a weight average molecular weight in terms of polystyrene of 1,000 to 100,000. [5] A resin composition containing a polyether compound according to any one of [1] to [4] and a curable compound having a structure different from that of any one of the polyether compounds according to [1] to [4]. [6] The resin composition according to [5], wherein the curable compound is a compound represented by formula (1) when l is 1 and m and n are 0. [7] The resin composition according to [5] or [6], further comprising a curing accelerator. [8] The resin composition of any one of [5] to [7], wherein the curable compound has at least one substituent selected from the group consisting of an epoxy group, an ester group, an oxazine group, a cyanate group, a maleimide group, an acryloyl group, a methacryloyl group, a styryl group, an allyl group, a vinyl group, a propenyl group, and a benzoxazine group. [9] The resin composition of any one of [5] to [8], further comprising an antioxidant.

[10] A cured product of the resin composition of any one of [5] to [9].

[11] A build-up film comprising the cured product of

[10] .

[12] A copper-clad laminate comprising the cured product of

[10] .

[13] A laminate comprising the cured product of

[10] .

[14] An electric or electronic component comprising the cured product of

[10] .

[15] An electric or electronic component having the laminate of

[13] .

[16] Use of the resin composition of any one of [5] to [9] as a raw material for an electric or electronic component.

[17] A method for producing a polyether compound according to any one of [1] to [4], comprising a step of reacting a phenol compound, a divalent aromatic halomethyl compound, and a monovalent ethylenically unsaturated double bond-containing compound in the presence of a basic compound.

[0022] According to the present invention, a polyether compound having excellent solvent solubility and capable of providing a cured product having low dielectric properties and excellent metal adhesion in a higher frequency environment can be obtained. Also, a resin composition capable of providing a cured product having low dielectric properties and excellent metal adhesion in a higher frequency environment, a cured product having low dielectric properties and excellent metal adhesion in a higher frequency environment, a laminate including the cured product, an electric / electronic component including the cured product, and an electric / electronic component having the laminate can be obtained.

[0023] Furthermore, the resin composition of the present invention can be suitably used for (multilayer) printed wiring boards, laminates for electric and electronic circuits such as capacitors, adhesives such as film adhesives and liquid adhesives, semiconductor encapsulating materials, underfill materials, interchip fills for 3D-LSIs, insulating sheets, prepregs, heat dissipation substrates, and the like.

[0024] An embodiment of the present invention will be described in detail below, but the following description is merely an example of an embodiment of the present invention, and the present invention is not limited to the following description as long as it does not deviate from the gist of the present invention. When an expression "to" is used in this specification, it is used as an expression including the numerical values ​​or physical property values ​​before and after it. In the present invention, for example, a description such as "at least one selected from the group consisting of XX, YY, and ZZ" means any of XX, YY, ZZ, a combination of XX and YY, a combination of XX and ZZ, a combination of YY and ZZ, or a combination of XX, YY, and ZZ.

[0025] [Polyether Compound] The polyether compound according to this embodiment is a polyether compound represented by the following formula (1) (hereinafter, may be referred to as "compound (1)").

[0026]

[0027] In formula (1), l and n represent 0 or 1, m represents an integer of 1 to 50, and Ar １ each independently represents an aromatic hydrocarbon group having 6 to 100 carbon atoms and not having a structure represented by formula (2), Ar ２represents a structure represented by formula (3) or a structure represented by formula (4) when m is 1 and n is 0, and when m is 2 to 50 or n is 1, each independently represents at least one structure selected from the group consisting of a structure represented by formula (3) and a structure represented by formula (4), and each Y independently represents a group containing an ethylenically unsaturated double bond and having 3 to 50 carbon atoms.

[0028]

[0029] In formulas (2) to (4), the symbol "*" represents a bond, and A １ ~A １０ are each independently any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group, and a naphthyl group, and R １ ~R ８ are each independently any one selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms.

[0030] The cured product of the resin composition containing the polyether compound according to the present embodiment exhibits the effect of having low dielectric properties and excellent metal adhesion. This is because the polyether compound contains an ortho-xylene moiety and / or a meta-xylene moiety, i.e., Ar, which has a small dipole moment and moderate flexibility, in formula (1). ２ Two oxymethylenes (-CH ２ This is presumably because the polyether compound according to this embodiment has a structure in which the bonding positions of the Ar—O—) chains are in the ortho and / or meta positions. ２ is a structure represented by the above formula (3), that is, Ar ２ It is particularly preferred that the bonding positions of the two oxymethylene chains to the benzene ring in the copolymer are in a meta-position relationship.

[0031] R １ ~R ８ Examples of the hydrocarbon group having 1 to 20 carbon atoms in the formula include a monovalent chain aliphatic hydrocarbon group, a monovalent cyclic aliphatic hydrocarbon group, and a monovalent aromatic hydrocarbon group.

[0032] Examples of the monovalent chain aliphatic hydrocarbon group include alkyl groups (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, n-hexyl, isohexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, and n-dodecyl groups), alkenyl groups (e.g., vinyl group, 1-propenyl group, 2-propenyl group, 1-methylvinyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1,3-butadienyl group, cyclohexenyl group, cyclohexadienyl group, cinnamyl group, naphthylvinyl group, etc.), and alkynyl groups (for example, ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1,3-butadienyl group, phenylethynyl group, naphthylethynyl group, etc.).

[0033] Examples of the monovalent alicyclic hydrocarbon group include a cyclohexyl group, a cycloheptyl group, a methylcyclohexyl group, a cyclooctyl group, a 3,3,5-trimethylcyclohexyl group, a cyclodecyl group, a cyclododecyl group, a norbornyl group, an adamantyl group, and a norbornylenyl group.

[0034] Examples of the monovalent aromatic hydrocarbon group include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, an ethylphenyl group, a styryl group, a xylyl group, an n-propylphenyl group, an isopropylphenyl group, a mesityl group, an ethynylphenyl group, a naphthyl group, a vinylnaphthyl group, a benzyl group, a methylbenzyl group, a dimethylbenzyl group, a trimethylbenzyl group, a naphthylmethyl group, a phenethyl group, and a 2-phenylisopropyl group.

[0035] R １ ~R ８Examples of the alkoxy group in the formula (I) include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, an n-pentoxy group, an isopentoxy group, a neopentoxy group, a tert-pentoxy group, a cyclopentoxy group, an n-hexyloxy group, an isohexyloxy group, a cyclohexyloxy group, an n-heptoxy group, a cycloheptoxy group, a methylcyclohexyloxy group, and a methylcyclohexyloxy group. Examples of the alkyl group include a silyl group, an n-octyloxy group, a cyclooctyloxy group, an n-nonyloxy group, a 3,3,5-trimethylcyclohexyloxy group, an n-decyloxy group, a cyclodecyloxy group, an n-undecyloxy group, an n-dodecyloxy group, a cyclododecyloxy group, a benzyloxy group, a methylbenzyloxy group, a dimethylbenzyloxy group, a trimethylbenzyloxy group, a naphthylmethoxy group, a phenethyloxy group, and a 2-phenylisopropoxy group.

[0036] R １ ~R ８ are preferably each independently any one selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 12 carbon atoms, more preferably each independently any one selected from the group consisting of a hydrogen atom and an aliphatic hydrocarbon group having 1 to 12 carbon atoms, and even more preferably each independently any one selected from the group consisting of a hydrogen atom and an aliphatic hydrocarbon group having 1 to 6 carbon atoms, because raw materials are easily available and this is industrially advantageous.

[0037] In formula (1), Ar １ The aromatic hydrocarbon group in the formula (5) is preferably at least one group selected from the group consisting of groups represented by formulas (5) to (8). In particular, from the viewpoint of obtaining a cured product that can more effectively exhibit excellent metal adhesion, Ar １ is more preferably a structure represented by formula (5) or formula (6), and from the viewpoint of obtaining a cured product that can better exhibit the effects of low dielectric properties and excellent metal adhesion, Ar １ is particularly preferably a structure represented by formula (5). Therefore, in the polyether compound having a structure represented by formula (1) according to the present invention, Ar １ is a structure represented by formula (5), and Ar２ However, it is particularly preferable that the structure be represented by formula (3).

[0038]

[0039] In formulas (5) to (8), the symbol "*" represents a bond, and X ４ represents a direct bond, a divalent hydrocarbon group having 1 to 20 carbon atoms, —O—, —S—, —CO—, —C(O)—O—, —C(O)—NH—, —SO—, or —SO ２ -, -C(CF ３ ) ２ - and -P(O)-, X5 is a trivalent hydrocarbon group having 1 to 20 carbon atoms, and X ６ is a tetravalent hydrocarbon group having 1 to 20 carbon atoms, and R ９ ~R ５０ are each independently any one selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms, and Z represents a structure represented by the following formula (9):

[0040]

[0041] In formula (9), the symbol "*" represents a bond, M represents an integer of 1 to 50, N represents 0 or 1, and Ar １ and Y is Ar in formula (1). １ and Y, and Ar ２ represents a structure represented by formula (3) or a structure represented by formula (4) when M is 1 and N is 0, or when M is 0 and N is 1, and represents at least one structure selected from the group consisting of a structure represented by formula (3) and a structure represented by formula (4) when M is 2 to 50, or when M is 1 and N is 1, independently.

[0042] In formula (5), R ９ ~R １６ are R in formula (3) and formula (4), respectively. １ ~R ８From the viewpoint of easy availability of raw materials and industrial advantages, and from the viewpoint of obtaining a cured product that can better exhibit effects such as low dielectric properties and excellent metal adhesion, preferably, R are each independently any one selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 12 carbon atoms, more preferably, R are each independently any one selected from the group consisting of a hydrogen atom and an aliphatic hydrocarbon group having 1 to 12 carbon atoms, and even more preferably, R are each independently any one selected from the group consisting of a hydrogen atom and an aliphatic hydrocarbon group having 1 to 6 carbon atoms, ９ ~R １６ Among these, it is particularly preferred that at least two groups are aliphatic hydrocarbon groups having 1 to 6 carbon atoms.

[0043] In formulas (6) to (8), R １７ ~R ５０ are R in formula (3) and formula (4), respectively. １ ~R ８ The same applies to the preferred ranges of each of these.

[0044] In formula (5), examples of the divalent hydrocarbon group having 1 to 20 carbon atoms include a divalent chain aliphatic hydrocarbon group, a divalent cyclic aliphatic hydrocarbon group, and a divalent cyclic aromatic hydrocarbon group. Examples of the divalent chain aliphatic hydrocarbon group include a methylene group, a 1,1-ethylene group, an isopropylidene group, a 1,2-ethylene group, a 1,3-propylene group, a 1,1-butylene group, a 1,4-butylene group, and a 1,3-dimethylbutylidene group.

[0045] Examples of the divalent alicyclic hydrocarbon group include a 1,1-cyclopentylene group, a 1,1-cyclohexylene group, a 3-methyl-1,1-cyclohexylene group, a 3,3,5-trimethyl-1,1-cyclohexylene group, a 1,1-cyclododecylene group, a 1,2-cyclopentylene group, a 1,2-cyclohexylene group, a 1,3-cyclopentylene group, a 1,3-cyclohexylene group, and a 1,4-cyclohexylene group.

[0046] Examples of the divalent cyclic aromatic hydrocarbon group include -CH(Ph)- and -C(CH ３ ) (Ph) -, -C (Ph)２ Examples of the alkyl group include 1,2-, 9,9-fluorenylene, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,3-phenylene-isopropylidene, 1,4-phenylenediisopropylidene, and a group represented by the following formula (10): In formula (10), the symbol "*" represents a bond. The above "Ph" means a phenyl group.

[0047]

[0048] X ４ is preferably any one selected from the group consisting of a direct bond, —O—, and a divalent hydrocarbon group having 1 to 13 carbon atoms, more preferably any one selected from the group consisting of a methylene group, a 1,1-ethylene group, an isopropylidene group, a 1,1-butylene group, a 1,3-dimethylbutylidene group, a 9,9-fluorenylene group, a 1,1-cyclohexylene group, a 3,3,5-trimethyl-1,1-cyclohexylene group, a 1,1-cyclododecylene group, and a 1,3-phenylenediisopropylidene group, and particularly preferably any one group selected from the group consisting of a methylene group, an isopropylidene group, a 1,1-butylene group, a 9,9-fluorenylene group, and a 1,3-phenylenediisopropylidene group. From the viewpoint of obtaining a cured product that can better exhibit the effects of low dielectric properties and excellent metal adhesion, in compound (1), Ar １ is a structure represented by formula (5), and X in formula (5) ４ is preferably any one group selected from the group consisting of an isopropylidene group, a 1,1-butylene group, and a 9,9-fluorenylene group. １ is a group represented by formula (5), and X in formula (5) ４ is any group selected from the group consisting of an isopropylidene group, a 1,1-butylene group, and a 9,9-fluorenylene group, and Ar ２ However, it is particularly preferable that the structure be represented by formula (3).

[0049] X ５Examples of the trivalent hydrocarbon group having 1 to 20 carbon atoms in the formula (11) include structures represented by the following formulas (11) to (16): The symbol "*" represents a bond.

[0050]

[0051] X ６ Examples of the tetravalent hydrocarbon group having 1 to 20 carbon atoms in the formula (17) include structures represented by the following formula (17):

[0052]

[0053] In formula (9), Ar １ , Ar ２ and Y are Ar in formula (1), respectively. １ , Ar ２ and Y. １ , Ar ２ The same applies to the preferred values ​​of and Y.

[0054] In formula (1), l and n represent 0 or 1, but from the viewpoint of obtaining a cured product that can better exhibit effects such as low dielectric properties and excellent metal adhesion, it is preferable that l is 1 and n is 0. m represents an integer of 1 to 50, but from the viewpoint of solvent solubility, it is preferably 1 to 30, more preferably 1 to 10.

[0055] In formula (9), N represents 0 or 1, but is preferably 0 from the viewpoint of obtaining a cured product that can better exhibit effects such as low dielectric properties and excellent metal adhesion. M represents an integer of 1 to 50, but is preferably 1 to 30, more preferably 1 to 10, from the viewpoint of solvent solubility.

[0056] In formula (1), examples of the group containing an ethylenically unsaturated double bond having 3 to 50 carbon atoms represented by Y include a 2-vinylbenzyl group, a 3-vinylbenzyl group, a 4-vinylbenzyl group, an allyl group, a methallyl group, a cinnamyl group, an acryloyl group, a methacryloyl group, a 2-allylphenyl group, a 2-propenylphenyl group, a 4-vinylphenyl group, a 4-isopropenylphenyl group, a 2-methoxy-4-allylphenyl group, and a 2-methoxy-4-propenylphenyl group. Preferably, the group contains at least one group selected from the group consisting of a 2-vinylbenzyl group, a 3-vinylbenzyl group, a 4-vinylbenzyl group, an allyl group, a methallyl group, a cinnamyl group, an acryloyl group, and a methacryloyl group. Among these, for reasons of easy availability of raw materials and industrial advantages, Y's are preferably each independently any group selected from the group consisting of a 3-vinylbenzyl group, a 4-vinylbenzyl group, an allyl group, a cinnamyl group, an acryloyl group, and a methacryloyl group, more preferably any group selected from the group consisting of a 3-vinylbenzyl group, a 4-vinylbenzyl group, an allyl group, and a methacryloyl group, and even more preferably any group selected from the group consisting of a 3-vinylbenzyl group, a 4-vinylbenzyl group, and a methacryloyl group.

[0057] <Method for producing compound (1)> There are no particular limitations on the method for producing compound (1), but compound (1) can be produced, for example, by a method including a step of using any phenol compound, a divalent aromatic halomethyl compound, and a monovalent ethylenically unsaturated double bond-containing compound as raw materials and reacting them in an organic solvent in the presence of a basic compound. The monovalent ethylenically unsaturated double bond-containing compound may be produced by polymerizing any phenol compound and a divalent aromatic halomethyl compound and then reacting them.

[0058] The phenol compound used as the raw material is not particularly limited as long as it has two or more aromatic rings, but is preferably a phenol compound having at least one structure selected from the group consisting of structures represented by formulas (18) to (21).

[0059]

[0060] In formulas (18) to (21), X ４ ~X ６ , R ９ ~R ５０ are X in formulas (5) to (8), respectively. ４ ~X ６ , R ９ ~R ５０ It is the same as X. ４ ~X ６ , R ９ ~R ５０ The same applies to the preferred ones of each of the above.

[0061] The phenol compounds may be used alone or in combination of two or more.

[0062] The divalent aromatic halomethyl compound used as the raw material is a compound (1) containing Ar ２ The compound is not particularly limited as long as it is a compound capable of introducing the structure shown above, and is preferably at least one compound selected from the group consisting of compounds represented by formula (22) and compounds represented by formula (23).

[0063]

[0064] In formula (22) and formula (23), R １ ~R ８ are R in formula (3) and formula (4), respectively. １ ~R ８ It is the same as R １ ~R ８ In the above formulas (22) and (23), Z each independently represents a halogen atom, and is preferably a chlorine atom or a bromine atom because raw materials are easily available and it is industrially advantageous.

[0065] From the viewpoint of the solvent solubility of the compound after production, the divalent aromatic halomethyl compound can be used in an amount of 0.5 to 4.0 times by mole, preferably 0.7 to 3.0 times by mole, per mole of hydroxyl groups of the starting phenol compound.

[0066] The divalent aromatic halomethyl compounds may be used alone or in combination of two or more.

[0067] Examples of the monovalent ethylenically unsaturated double bond-containing compound that can be used as a raw material include an ethylenically unsaturated double bond-containing halogenated compound and an ethylenically unsaturated double bond-containing phenol compound.

[0068] The ethylenically unsaturated double bond-containing halogenated compound is not particularly limited, and preferred examples thereof include 2-(chloromethyl)styrene, 3-(chloromethyl)styrene, 4-(chloromethyl)styrene, allyl chloride, allyl bromide, 2-methylallyl chloride, cinnamyl chloride, cinnamyl bromide, acrylic acid chloride, and methacrylic acid chloride, because raw materials are easily available and they are industrially advantageous.

[0069] The ethylenically unsaturated double bond-containing phenol compound is not particularly limited, and preferred examples thereof include 2-allylphenol, 2-propenylphenol, 4-vinylphenol, 4-isopropenylphenol, 2-methoxy-4-allylphenol, and 2-methoxy-4-propenylphenol because the raw materials are easily available and they are industrially advantageous.

[0070] From the viewpoint of efficiently proceeding with the reaction while reducing production costs, the monovalent ethylenically unsaturated double bond-containing phenol compound can be used in an amount of 0.05 to 1.0 times by mole, preferably 0.1 to 0.8 times by mole, per mole of hydroxyl groups of the phenol compound used as the raw material.

[0071] From the viewpoint of efficiently proceeding with the reaction while suppressing production costs, the monovalent ethylenically unsaturated double bond-containing halogenated compound can be used in an amount of 0.05 to 1.0 times by mole, preferably 0.1 to 0.8 times by mole, per mole of halogen atoms in the divalent aromatic halomethyl compound used as the raw material.

[0072] This reaction is preferably carried out in the presence of a basic compound. Examples of basic compounds include alkali metal hydroxides and alkali metal salts such as sodium hydroxide, potassium hydroxide, and potassium carbonate; amines such as diazabicyclononene, diazabicycloundecene, and triethylamine; sodium tert-butoxide, potassium tert-butoxide, lithium diisopropylamide, silicon-basic amines, and lithium tetramethylpiperidine. In terms of being relatively inexpensive and unlikely to cause side reactions, alkali metals, diazabicycloundecene, and potassium tert-butoxide are preferred, and sodium hydroxide, potassium hydroxide, and potassium carbonate are particularly preferred. One type of basic compound may be used alone, or two or more types may be used in combination. These basic compounds may also be used as aqueous or alcoholic solutions.

[0073] From the viewpoint of increasing the reaction rate and eliminating the need for removing excess alkali, thereby improving productivity, the amount of the basic compound used is preferably 0.7 to 3.0 times by mole, and more preferably 0.8 to 2 times by mole, per mole of hydroxyl groups in the starting phenol compound.

[0074] This reaction is preferably carried out in the presence of an organic solvent, and examples of the organic solvent include polar solvents.

[0075] Examples of polar solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, N,N-dimethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, methanol, ethanol, isopropanol, butanol, ethyl acetate, butyl acetate, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran. Acetone, N,N-dimethylformamide, N-methyl-2-pyrrolidone, and diethylene glycol dimethyl ether are preferred because of their relatively low cost and good reactivity. One organic solvent may be used alone, or two or more organic solvents may be used in combination. A low-polarity solvent such as toluene or xylene may also be used in combination. The reaction may also be carried out in the presence of water.

[0076] This reaction may be carried out in the presence of a phase transfer catalyst to promote the progress of the reaction. Examples of phase transfer catalysts include quaternary ammonium salts. Examples of quaternary ammonium salts include bromides, chlorides, iodides, hydrogen sulfates, and hydroxides of tetramethylammonium, trimethylethylammonium, dimethyldiethylammonium, triethylmethylammonium, tripropylmethylammonium, tributylmethylammonium, trioctylmethylammonium, tetraethylammonium, trimethylpropylammonium, trimethylphenylammonium, benzyltrimethylammonium, benzyltriethylammonium, diallyldimethylammonium, n-octyltrimethylammonium, stearyltrimethylammonium, cetyldimethylethylammonium, tetrapropylammonium, tetra-n-butylammonium, β-methylcholine, and phenyltrimethylammonium. Tetra-n-butylammonium salts are preferred because they are relatively inexpensive and have good reactivity.

[0077] More specifically, this reaction involves dissolving a phenolic compound, a divalent aromatic halomethyl compound, and a basic compound in an organic solvent and reacting them for 0.5 to 20 hours. Thereafter, a monovalent ethylenically unsaturated double bond-containing compound is added, and the reaction is continued for 0.5 to 20 hours. The reaction temperature is not particularly limited as long as it is a temperature at which the phenolic compound, the divalent aromatic halomethyl compound, and the monovalent ethylenically unsaturated double bond-containing compound react, and is preferably 10 to 150°C, and more preferably 40 to 130°C.

[0078] After the reaction, inorganic components are removed by methods such as washing with water and filtration, and the polyether compound of the present embodiment can be obtained by removing unreacted raw materials by distillation or the like, concentrating the product, purifying the product (recrystallization, reprecipitation, washing, column chromatography, etc.), etc. The number of times that water washing is performed is not particularly limited, but is preferably 1 to 6 times, and more preferably 1 to 4 times.

[0079] <Physical Properties of Polyether Compound> The polystyrene-equivalent weight average molecular weight (Mw) of the polyether compound of this embodiment is preferably 1,000 to 100,000, more preferably 1,500 to 50,000, and even more preferably 2,000 to 30,000. The polystyrene-equivalent number average molecular weight (Mn) of the polyether compound of this embodiment is preferably 500 to 50,000, more preferably 750 to 10,000, and even more preferably 1,000 to 5,000. Having Mw and Mn equal to or greater than the above-mentioned lower limits is preferable because a cured product with excellent low dielectric properties and metal adhesion can be obtained. Having Mw and Mn equal to or less than the above-mentioned upper limits is preferable because a polyether compound with excellent solubility in solvents and better handleability can be obtained. The Mw and Mn in the present invention are values ​​measured by gel permeation chromatography (GPC) under the conditions described in the Examples below.

[0080] [Resin Composition] One aspect of the resin composition according to this embodiment may contain at least the polyether compound according to this embodiment. The polyether compound according to this embodiment contained in the resin composition according to this embodiment may be used alone or in combination of two or more types. Another aspect of the resin composition according to this embodiment preferably further contains a curable compound (hereinafter also referred to as "curable compound (2)") having a structure different from that of the polyether compound according to this embodiment. A curing accelerator may also be contained. The resin composition according to this embodiment may contain other components in addition to the polyether compound and curable compound (2) according to this embodiment, or in addition to the polyether compound, curable compound (2), and curing accelerator according to this embodiment.

[0081] <Curable Compound (2)> The curable compound (2) is not particularly limited and is a compound that is cured by irradiation with heat or light (visible light, ultraviolet light, infrared light, etc.), and may be a compound that requires a curing accelerator described below upon curing.

[0082] As the curable compound (2), for example, a compound represented by formula (1) when l is 1 and m and n are 0 (hereinafter also referred to as "compound (3)"); or a compound having at least one substituent selected from the group consisting of an epoxy group, an ester group, an oxazine group, a cyanate group, a maleimide group, an acryloyl group, a methacryloyl group, a styryl group, an allyl group, a vinyl group, a propenyl group, and a benzoxazine group is preferably used. As the curable compound (2), for example, compound (3), a maleimide compound, a styryl compound, an acrylic compound, a methacrylic compound, a vinyl compound, an allyl compound, a propenyl compound, a cyanate compound, an oxazine compound, a benzocyclobutene compound, an epoxy compound, a phenol compound, an amine compound, an acid anhydride compound, and an active ester compound may be used. In view of the balance of dielectric properties, curability, and other physical properties, at least one compound selected from the group consisting of compound (3), maleimide compounds, styryl compounds, acrylic compounds, methacrylic compounds, vinyl compounds, and allyl compounds is preferred. One type of curable compound (2) may be used alone, or two or more types may be used in combination.

[0083] In the resin composition according to this embodiment, the content of the curable compound (2) is preferably 0.01 to 10,000 parts by mass, more preferably 0.05 to 5,000 parts by mass, and even more preferably 0.1 to 1,000 parts by mass, relative to 100 parts by weight of the compound (1). By making the content of the curable compound (2) in the resin composition equal to or greater than the above-mentioned lower limit, a cured product with excellent dielectric properties can be more easily obtained. Furthermore, by making the content of the curable compound (2) in the resin composition equal to or less than the above-mentioned upper limit, a uniform resin composition with excellent curability can be more easily obtained.

[0084] <Compound (3)> Compound (3) is a compound represented by the following formula (24a).

[0085]

[0086] In formula (24a), Ar １ and Y are Ar in formula (1), respectively.１ and Y. １ The same applies to the preferred values ​​of and Y.

[0087] In the resin composition according to this embodiment, the content of compound (3) is preferably 0.01 to 50 parts by mass, more preferably 0.05 to 30 parts by mass, and even more preferably 0.1 to 20 parts by mass, per 100 parts by weight of compound (1). By ensuring that the content of compound (3) in the resin composition is equal to or greater than the above-mentioned lower limit, a cured product can be obtained that can better exhibit effects such as excellent metal adhesion. Furthermore, by ensuring that the content of curable compound (2) in the resin composition is equal to or less than the above-mentioned upper limit, a cured product with excellent heat resistance can be obtained.

[0088] <Maleimide Compound> The maleimide compound is a compound having at least one maleimide group in the molecule. The maleimide compound preferably has one or more maleimide groups per molecule, and more preferably has two or more maleimide groups. These may be used alone or in combination of two or more.

[0089] Examples of the maleimide compound include "BMI-1100" (formula 24-1 below), "BMI-2300" (formula 24-2 below), and "BMI-TMH" (formula 24-3 below) manufactured by Daiwa Chemical Industry Co., Ltd., "BMI-70" (formula 24-4 below) and "BMI-80" (formula 24-5 below) manufactured by KI Chemical Industry Co., Ltd., "MIR-3000" (formula 24-6 below) and "MIR-5000" (formula 24-7 below) manufactured by Nippon Kayaku Co., Ltd., and "BMI-1100" (formula 24-1 below) and "BMI-2300" (formula 24-2 below) manufactured by Designer's Chemical Industry Co., Ltd. Examples of such compounds include compounds represented by "BMI-689" (formula 24-8 below), "BMI-1500" (formula 24-9 below), "BMI-1700" (formula 24-10 below), "BMI-3000", and "BMI-5000" (formula 24-11 below) and (formula 24-12 below), all of which are manufactured by Molecules.

[0090]

[0091]

[0092]

[0093] In the formulas (24-2), (24-6), (24-9), (24-10), (24-11), and (24-12), n is each independently an integer of 1 to 50.

[0094] <Styryl Compound> A styryl compound is a compound having at least one styryl group in the molecule. The styryl compound preferably has one or more styryl groups per molecule, and more preferably has two or more styryl groups. These may be used alone or in combination of two or more.

[0095] The styryl compound is not particularly limited, but examples thereof include polycondensates of phenol compounds and chloromethylstyrene, which will be described later.

[0096] Examples of the styryl compound include "OPE-2st" (formula 25-1) manufactured by Mitsubishi Gas Chemical Company, Inc., and compounds represented by formulae (25-2) to (25-4).

[0097]

[0098] In the above formulas (25-1) and (25-4), n is each independently an integer of 0 to 300. In the above formula (25-3), n is an integer of 0 to 10.

[0099] <Acrylic Compound and Methacrylic Compound> The acrylic compound and methacrylic compound are compounds containing an acryloyl group and a methacryloyl group. The acrylic compound and methacrylic compound preferably have one or more acryloyl groups and methacryloyl groups per molecule, and more preferably have two or more acryloyl groups and methacryloyl groups per molecule. These may be used alone or in combination of two or more.

[0100] Examples of acrylic compounds and methacrylic compounds include "SA9000" (formula 26-1 below) manufactured by SABIC, "NK Ester DCP" (formula 26-2 below) manufactured by Shin-Nakamura Chemical Co., Ltd., "DCP-A" manufactured by Kyoeisha Chemical Co., Ltd., and "NPDGA," "FM-400," "R-687," "THE-330," "PET-30," and "DPHA" manufactured by Nippon Kayaku Co., Ltd.

[0101]

[0102] In the above formula (26-1), n ​​is each independently an integer of 0 to 300.

[0103] <Vinyl Compound> The vinyl compound is a compound containing a vinyl group. The vinyl compound preferably has one or more vinyl groups per molecule, and more preferably has two or more vinyl groups. These may be used alone or in combination of two or more.

[0104] Examples of vinyl compounds include "Ricon 100," "Ricon 181," and "Ricon 184" (formula 27-1 below) manufactured by Cray Valley Corporation, and "B-1000" (formula 27-2 below) and "JP-100" (formula 27-3 below) manufactured by Nippon Soda Co., Ltd.

[0105]

[0106] In the above formulas (27-1) to (27-3), l, m, and n each independently represent an integer of 0 to 5,000.

[0107] <Allyl Compound> An allyl compound is a compound having an allyl group (CH ２ =CH-CH ２ The allyl compound preferably has one or more allyl groups per molecule, and more preferably has two or more allyl groups. These compounds may be used alone or in combination of two or more.

[0108] Examples of the allyl compound include allyl phenol compounds such as "DABPA" (formula 28-1 below) manufactured by Daiwa Kasei Co., Ltd., "MEH-8000H" and "MEH-8005" manufactured by Meiwa Kasei Co., Ltd., "SBA", "APG", "LVA", and "FATC" manufactured by Gun-ei Chemical Industry Co., Ltd., "TAIC" (formula 28-2 below) manufactured by Mitsubishi Chemical Corporation, and "L-DAIC", "DD-1", "TA-G", and "P-DAIC" manufactured by Shikoku Chemical Industry Co., Ltd., isocyanuric ring-containing allyl compounds such as "DAD" (formula 28-3 below) manufactured by Nisshoku Techno Fine Chemical Co., Ltd., allyl ester compounds such as "FTC-AE" manufactured by Gun-ei Chemical Industry Co., Ltd., and bisallylnadiimide compounds such as "BANI-M" (formula 28-4 below) and "BANI-X" (formula 28-5 below) manufactured by Maruzen Petrochemical Co., Ltd.

[0109]

[0110] <Propenyl Compound> The propenyl compound is a compound containing a propenyl group. The propenyl compound preferably has one or more propenyl groups per molecule, and more preferably has two or more propenyl groups. These may be used alone or in combination of two or more.

[0111] Examples of the propenyl compound include "BPN" manufactured by Gun-ei Chemical Co., Ltd. and "Compimide™123" manufactured by Evonik (see formula 29 below).

[0112]

[0113] <Benzocyclobutene Compound> An example of the benzocyclobutene compound is "CYCLOTENE" (formula 30 below) manufactured by Dow Chemical Company.

[0114]

[0115] <Oxazine Compound> Examples of the oxazine compound include "P-d" (formula 31-1 below), "ALP-d" (formula 31-2 below), and "F-a" (formula 31-3 below) manufactured by Shikoku Chemical Industry Co., Ltd., and "BTBz" (formula 31-4 below) manufactured by Japan Material Technology Co., Ltd. These may be used alone or in combination of two or more.

[0116]

[0117]

[0118] <Cyanate Compound> Examples of the cyanate compound include compounds represented by the following formulas (32-1) to (32-7). These may be used alone or in combination of two or more.

[0119]

[0120]

[0121] In formulas (32-5) to (32-7), n each independently represents an integer of 1 to 50.

[0122] <Epoxy Compound> Examples of epoxy compounds include bisphenol A type epoxy resins, bisphenol C type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, phenol novolac type epoxy resins, tert-butyl-catechol type epoxy resins, naphthol type epoxy resins, naphthalene type epoxy resins, naphthylene ether type epoxy resins, glycidylamine type epoxy resins, glycidyl ester type epoxy resins, cresol novolac type epoxy resins, biphenyl type epoxy resins, anthracene type epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, cyclohexanedimethanol type epoxy resins, trimethylol type epoxy resins, and halogenated epoxy resins. The epoxy resin may contain a polymeric epoxy resin or a phenoxy resin. These may be used alone or in combination of two or more.

[0123] <Phenol Compound> Examples of phenol compounds include various polyhydric phenols such as bisphenols, biphenols, hydroquinones, dihydroxynaphthalenes, phenol novolac resins, cresol novolac resins, phenol aralkyl resins, biphenyl aralkyl resins, naphthol aralkyl resins, terpene phenol resins, dicyclopentadiene phenol resins, bisphenol A novolac resins, trisphenolmethane resins, and naphthol novolac resins, as well as polyhydric phenol resins obtained by condensation reactions of various phenols with aldehydes and polyhydric phenol resins obtained by condensation reactions of xylene resins and phenols. These may be used alone or in combination of two or more.

[0124] <Amine Compound> Examples of the amine compound include aliphatic amines, polyether amines, alicyclic amines, and aromatic amines. These may be used alone or in combination of two or more.

[0125] <Acid Anhydride Compound> Examples of the acid anhydride compound include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, etc. These may be used alone or in combination of two or more.

[0126] <Active Ester Compound> The active ester compound is not particularly limited, but generally, compounds having two or more highly reactive ester groups per molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, are preferably used. The active ester resin is preferably one obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester resin obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester resin obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferred. These may be used alone or in combination of two or more.

[0127] Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalene, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-type diphenol compounds, and phenol novolak. Here, the "dicyclopentadiene type diphenol compound" is a diphenol compound obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

[0128] Specifically, an active ester resin containing a dicyclopentadiene-type diphenol structure, an active ester resin containing a naphthalene structure, an active ester resin containing an acetylated product of phenol novolac, or an active ester resin containing a benzoylated product of phenol novolac is preferred, and an active ester resin containing a naphthalene structure or an active ester resin containing a dicyclopentadiene-type diphenol structure is more preferred. Here, the "dicyclopentadiene-type diphenol structure" refers to a divalent structural unit consisting of phenylene-dicyclopentalene-phenylene.

[0129] <Other Components> The resin composition according to this embodiment may contain components other than those listed above (sometimes referred to as "other components" in the present invention) for the purpose of further improving its functionality. Examples of other components include elastomers, curing accelerators, antioxidants, polymerization inhibitors, inorganic fillers, organic fillers, ultraviolet protection agents, coupling agents, plasticizers, fluxes, flame retardants, colorants, dispersants, emulsifiers, elasticity reducing agents, diluents, antifoaming agents, and ion trapping agents.

[0130] <Elastomer> The resin composition according to this embodiment may contain an elastomer to further improve the low dielectric properties and metal adhesion of the cured product. Examples of elastomers include styrene-based elastomers, olefin-based elastomers, urethane-based elastomers, polyester-based elastomers, polyamide-based elastomers, acrylic elastomers, and silicone-based elastomers. These elastomers are composed of hard segment components and soft segment components, and generally, the hard segment components contribute to heat resistance and strength, while the soft segment components contribute to flexibility and toughness. One type of elastomer may be used alone, or two or more types may be used in combination.

[0131] As the elastomer, from the viewpoint of dielectric dissipation factor (tan δ), a styrene-based elastomer is preferred, and a styrene-based thermoplastic elastomer is more preferred. The styrene-based elastomer may have a structural unit derived from a styrene-based compound. From the viewpoints of dielectric dissipation factor (tan δ), metal adhesion, heat resistance, and low thermal expansion, one or more types selected from the group consisting of hydrogenated styrene-butadiene-styrene block copolymers (SEBS, SBBS), hydrogenated styrene-isoprene-styrene block copolymers (SEPS), and styrene-maleic anhydride copolymers (SMA) are preferred, one or more types selected from the group consisting of SEBS and SEPS are more preferred, and SEBS is even more preferred. The elastomer may be used alone or in combination of two or more types.

[0132] <Curing Accelerator> The resin composition according to the present embodiment preferably contains a curing accelerator. By including a curing accelerator, it is possible to shorten the curing time and lower the curing temperature, making it easier to obtain a desired cured product.

[0133] The curing accelerator is not particularly limited, and examples thereof include thermal or photoradical curing accelerators, cationic curing accelerators, anionic curing accelerators, and transition metal compounds.

[0134] Examples of the thermal radical curing accelerator include organic peroxides such as dicumyl peroxide, di(tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, di-tert-amyl peroxide, di-tert-hexyl peroxide, and benzoyl peroxide; and azo compounds such as azobisbutyronitrile, 1,1'-azobis(1-acetoxy-1-phenylethane), 2,2'-azobis(2,4-dimethylvaleronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), dimethyl-2,2'-azobis(isobutyrate), and 2,2'-azobis(2-methylbutyronitrile).

[0135] Examples of the cationic curing accelerator include diaryliodonium salts having BF4, PF6, and SbF6 as anions, trialkylphosphonium salts, phosphonium salts such as butyltriphenylphosphonium thiocyanate, and boron trifluoride.

[0136] Examples of the anionic curing accelerator include 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-ethylimidazole, 2,4-dimethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-vinyl-2-methylimidazole, 1-propyl-2-methylimidazole, and 2-isopropylimidazole. imidazole compounds such as propyl imidazole, 1-cyanomethyl-2-methyl-imidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, and 1-cyanoethyl-2-phenylimidazole; amine compounds such as 1,8-diaza-bicyclo(5,4,0)undecene-7,4-dimethylaminopyridine; phosphine compounds such as triphenylphosphine; and quaternary phosphonium salt compounds such as triphenylbenzylphosphonium salts, triphenylethylphosphonium salts, and tetrabutylphosphonium salts.

[0137] Examples of the transition metal compound include zinc compounds (transition metal salts) such as tin octylate, zinc carboxylate (zinc 2-ethylhexanoate, zinc stearate, zinc behenate, zinc myristylate), and zinc phosphate esters (zinc octylphosphate, zinc stearylphosphate, etc.).

[0138] The curing accelerator is preferably a thermal radical curing accelerator or an anionic curing accelerator, and more preferably a thermal radical curing accelerator. The curing accelerator may be used alone or in combination of two or more kinds.

[0139] The amount of the curing accelerator is preferably 0.0001 parts by weight or more, more preferably 0.001 parts by weight or more, and even more preferably 0.005 parts by weight or more, per 100 parts by weight of the resin composition, and is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, and even more preferably 5 parts by weight or less. The above upper and lower limits can be arbitrarily combined. For example, it may be 0.0001 parts by weight or more and 20 parts by weight or less, 0.001 parts by weight or more and 10 parts by weight or less, or 0.005 parts by weight or more and 5 parts by weight or less. When the content of the curing accelerator is equal to or greater than the above lower limit, a good curing acceleration effect can be obtained. On the other hand, when it is equal to or less than the above upper limit, it is preferable because the desired cured physical properties are easily obtained.

[0140] <Solvent> The resin composition according to this embodiment may be diluted by blending any solvent to adjust the viscosity appropriately. In the resin composition according to this embodiment, the solvent is used to ensure the handling and workability in molding the resin composition, and there is no particular limit to the amount used. In the present invention, the term "solvent" and the aforementioned term "solvent" are used to distinguish between them depending on the form of use, but the same or different solvents may be used independently.

[0141] Examples of the solvent include ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, and cyclohexanone, esters such as γ-butyrolactone and ethyl acetate, ethers such as ethylene glycol monomethyl ether, amides such as N,N-dimethylformamide and N,N-dimethylacetamide, alcohols such as methanol and ethanol, alkanes such as hexane and cyclohexane, and aromatics such as toluene, xylene, and anisole. The solvent may be used alone or in combination of two or more.

[0142] The content of the solvent in the resin composition is not particularly limited, but is preferably in the range of 0 to 2000 parts by weight, more preferably 1000 parts by weight or less, per 100 parts by weight of the resin composition.

[0143] <Antioxidant> Examples of the antioxidant include hindered phenol compounds, phosphorus compounds, sulfur compounds, metal compounds, and hindered amine compounds, with hindered phenol compounds being preferred.

[0144] The hindered phenol compound is preferably a compound having a molecular weight of 500 or more. Examples of the hindered phenol compound having a molecular weight of 500 or more include triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-3,5-triazine, pentaerythritol tetrakis[3-(3,5-t-butyl-4-hydroxyphenyl)propionate], and the like. bis(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 1,1,3-tris[2-methyl-4-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]-5-t-butylphenyl]butane, 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, N,N-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 1,3, 5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 2,6-di-tert-butyl-p-cresol (BHT), 1,3,5-tris(3,5-di-t (1H,3H,5H)-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione [manufactured by ADEKA Corporation, AO-020], 4,4',4''-(1-methylpropanyl-3-ylidene)tris(6-tert-butyl-m-cresol) [manufactured by ADEKA Corporation, AO-030], 6,6'-di-tert-butyl-4,4'-butylidenedi-m-cresol [manufactured by ADEKA Corporation, AO-040],1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene [manufactured by ADEKA Corporation, AO-330] is an example.

[0145] Examples of the hindered amine compound include 2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxyl [ADEKA CORPORATION, Adeka STAB LA-7RD], IRGASTAB UV 10 (4,4'-[1,10-dioxo-1,10-decanediyl)bis(oxy)]bis[2,2,6,6-tetramethyl]-1-piperidinyloxy) (CAS. 2516-92-9), TINUVIN 123 (4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl) (all manufactured by BASF), FA-711HM, FA-712HM (2,2,6,6-tetramethylpiperidinyl methacrylate, manufactured by Showa Denko Materials K.K.), TINUVIN 111FDL, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN 765, TINUVIN 770DF, TINUVIN 5100, SANOL LS-2626, CHIMASSORB 119FL, CHIMASSORB 2020 FDL, CHIMASSORB 944 FDL, TINUVIN 622 LD (all manufactured by BASF), LA-52, LA-57, LA-62, LA-63P, LA-68LD, LA-77Y, LA-77G, LA-81, LA-82 (1,2,2,6,6-pentamethyl-4-piperidyl methacrylate), and LA-87 (all manufactured by ADEKA Corporation).

[0146] The content of the antioxidant in the resin composition is not particularly limited, but it is preferably used in the range of 0.001 parts by weight to 10 parts by weight per 100 parts by weight of the resin composition.

[0147] <Polymerization Inhibitor> Examples of the polymerization inhibitor include quinones such as hydroquinone, methylhydroquinone, p-benzoquinone, chloranil, and trimethylquinone, and phenols such as 4-tert-butylpyrocatechol, p-methoxyphenol, and 2,6-di-tert-4-methylphenol.

[0148] [Cured Product] The cured product obtained by curing the resin composition according to this embodiment has an excellent balance between low dielectric properties and high metal adhesion, and exhibits good cured physical properties. "Curing" here means intentionally curing the resin composition by heat and / or light, etc., and the degree of curing may be controlled depending on the desired physical properties and application. The degree of progress may be completely cured or semi-cured.

[0149] The method for curing the resin composition according to this embodiment varies depending on the components and their amounts in the resin composition, but preferably includes curing under heating conditions of 60 to 280°C for 1 to 600 minutes. The heating temperature is more preferably 100 to 250°C, and even more preferably 120 to 230°C. The heating time is more preferably 5 to 450 minutes, and even more preferably 30 to 300 minutes.

[0150] When producing a semi-cured resin product, it is preferable to proceed with the curing reaction of the resin composition to an extent that the shape can be maintained by heating, etc. When the resin composition contains a solvent, most of the solvent is usually removed by techniques such as heating, decompression, air drying, etc., but 5 parts by weight or less of the solvent may remain in the semi-cured resin product.

[0151] [Laminate] The laminate according to this embodiment may be a laminate of a layer containing the resin composition according to this embodiment and a substrate. It is sufficient that the resin composition according to this embodiment is used in at least one layer in the laminate according to this embodiment, and layers made of two or more resin compositions may be formed. Furthermore, when a substrate is used in the laminate, two or more types of substrates may be used. The thickness of the layer made of the resin composition in the laminate is, for example, typically 1 μm to 3 mm.

[0152] The layer containing the resin composition according to the present embodiment may be a prepreg obtained by impregnating a nonwoven fabric or cloth made of inorganic and / or organic fiber materials such as glass fiber, polyester fiber, aramid fiber, cellulose, nanofiber cellulose, etc. with the resin composition of the present invention and curing the impregnated fabric or cloth. Alternatively, the layer may be a cured film obtained by melt molding or cast molding the resin composition.

[0153] From the viewpoint of adhesiveness and practicality, examples of the substrate include inorganic substrates, metal substrates, resin substrates, and prepregs.

[0154] Examples of inorganic substrates include substrates containing at least one selected from the group consisting of glass, silicon, alumina, silicon carbide, gallium nitride, silicon nitride, and the like.

[0155] Examples of the metal substrate include a substrate containing at least one selected from the group consisting of copper, aluminum, gold, silver, nickel, palladium, etc. Metal foils of these metals, or metal layers formed by plating or sputtering, can also be used as the metal substrate.

[0156] Examples of resin substrates include substrates containing at least one selected from the group consisting of liquid crystal polymer, polyimide, polyphenylene sulfide, polyether ether ketone, polyamide, polyethylene terephthalate, polyethylene naphthalate, cycloolefin polymer, and polyolefin.

[0157] [Uses] The compound, resin composition, cured product, and laminate according to this embodiment can be used in a variety of fields, such as adhesives, paints, civil engineering and construction materials, various composite materials including carbon fiber reinforced plastics (CFRP), and insulating materials for electric and electronic components, and are particularly useful as insulating casting materials for electric and electronic components, laminate materials, sealing materials, etc. Specific examples include (multilayer) printed wiring boards, copper-clad laminates, build-up films, laminates for electric and electronic circuits such as capacitors, adhesives such as film adhesives and liquid adhesives, semiconductor sealing materials, underfill materials, interchip fills for 3D-LSI, insulating sheets, prepregs, and heat dissipation substrates, but are not limited to these.

[0158] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Note that the values ​​of various production conditions and evaluation results in the following examples represent preferred upper or lower limit values ​​in the embodiments of the present invention, and a preferred range may be defined by a combination of the above-mentioned upper or lower limit values ​​and the values ​​in the following examples or values ​​between the examples.

[0159] [Methods for Evaluating Physical Properties and Characteristics] In the following synthesis examples, examples, and comparative examples, the physical properties and characteristics were evaluated by the methods described below.

[0160] <1> Weight-average molecular weight (Mw), number-average molecular weight (Mn) of polyether compound, and weight ratio of compound (1) to compound (3) (curable compound (2)) Using an "HLC-8320 GPC apparatus" manufactured by Tosoh Corporation, under the following measurement conditions, standard polystyrenes were used: TSK Standard Polystyrene: F-128 (Mw: 1,090,000, Mn: 1,030,000), F-10 (Mw: 106,000, Mn: 103,000), F-4 (Mw: 43,000, Mn: 42,700), F-2 (Mw: 17,200, Mn: 16,900). A calibration curve was created using A-5000 (Mw: 6,400, Mn: 6,100), A-2500 (Mw: 2,800, Mn: 2,700), A-1000 (Mw: 1,100, Mn: 871), and A-300 (Mw: 453, Mn: 387), and the weight average molecular weight (Mw), number average molecular weight (Mn), and the weight ratio of compound (1) to compound (3) (curable compound (2)) were measured as polystyrene equivalent values.

[0161] Column: "TSKGEL Super HM-H + H5000 + H4000 + H3000 + H2000" manufactured by Tosoh Corporation Eluent: tetrahydrofuran Flow rate: 0.5 ml / min Detection: UV (wavelength 254 nm) Temperature: 40°C Sample concentration: 0.1 wt% Injection volume: 10 μL

[0162] <2> Dielectric Loss Tangent of Cured Product The film-like cured product was cut into test pieces 2 mm wide and 90 mm long, and the dielectric loss tangent at 10 GHz was measured by the split cylinder method using a network analyzer (N5224B, manufactured by KEYSIGHT TECHNOLOGIES) and a cavity resonator (CP531, manufactured by Kanto Electronics Application Development Co., Ltd.).

[0163] <3> Copper Foil Peel Strength To evaluate the metal adhesion of the cured product, the copper foil peel strength was measured using the following procedure. That is, a varnish-like resin composition was applied to copper foil (manufactured by Mitsui Mining & Smelting Co., Ltd., product name "3EC-M3-VLP") using an applicator and dried at 130°C for 5 minutes to form a coating film of the resin composition. Copper foil (manufactured by Mitsui Mining & Smelting Co., Ltd., product name "3EC-M3-VLP") was placed on the resulting coating film and vacuum pressed at 200°C and 0.2 MPa for 2 hours to produce a copper foil-attached cured film. The resulting copper foil-attached cured film was cut into a width of 2.5 cm and a length of 20 cm and subjected to a 180° peel test at a tensile speed of 50 mm / min using an Instron tensile tester in an atmosphere of 23°C and 50% relative humidity. The median value was recorded as the adhesive strength of the cured film to the copper foil (copper foil peel strength) (N / cm).

[0164] [Synthesis Example 1] A 500 mL four-neck flask equipped with a thermometer, a stirrer, and a condenser was charged with 15 g (0.059 mol) of bisphenol C (manufactured by Honshu Chemical Co., Ltd., product name "S-BOC"), 6.8 g (0.039 mol), 9.3 g (0.14 mol) of potassium hydroxide (purity 85%), 0.63 g of tetrabutylammonium bromide, and 30 g of diethylene glycol dimethyl ether. The reaction temperature was raised to 75 ° C., and the reaction was carried out for 3 hours. Thereafter, 7.14 g (0.047 mol) of 4-(chloromethyl)styrene (manufactured by AGC Seimi Chemical Co., Ltd., product name "CMS-14") was added, and the reaction was carried out for another 3 hours at 75 ° C. After completion of the reaction, 30 g of toluene was added, and the mixture was washed four times with 100 g of water. Thereafter, 300 g of isopropyl alcohol was added, and the precipitated solid was separated by filtration. The obtained solid was washed three times with 100 g of isopropyl alcohol and dried to obtain 16 g of a resin composition of compound (1-1) represented by the following formula (33) and compound (3-1) represented by the following formula (34). The weight average molecular weight of compound (1-1) was 7876 and the number average molecular weight was 1236. The content of compound (3-1) in the obtained resin composition was 26 wt %.

[0165]

[0166]

[0167] Synthesis Example 2: A 500 mL four-neck flask equipped with a thermometer, a stirrer, and a condenser was charged with 15 g (0.059 mol) of bisphenol C (manufactured by Honshu Chemical Co., Ltd., product name "S-BOC"), 9.3 g (0.14 mol) of potassium hydroxide (purity 85%), 0.63 g of tetrabutylammonium bromide, and 45 g of diethylene glycol dimethyl ether, and the mixture was stirred at room temperature for 1 hour. 6.8 g (0.039 mol) of m-xylene dichloride was added, and the reaction temperature was raised to 75°C, after which the reaction was carried out for 3 hours. Thereafter, 7.14 g (0.047 mol) of 4-(chloromethyl)styrene (manufactured by AGC Seimi Chemical Co., Ltd., product name "CMS-14") was added, and the reaction was carried out for an additional 3 hours at 75°C. After completion of the reaction, 30 g of toluene was added, and the mixture was washed four times with 100 g of water. Thereafter, 300 g of isopropyl alcohol was added, and the precipitated solid was separated by filtration. The obtained solid was washed three times with 100 g of isopropyl alcohol and dried to obtain 16 g of a resin composition of compound (1-2) represented by formula (33) and compound (3-1) represented by formula (34). The weight average molecular weight of compound (1-2) was 2766, and the number average molecular weight was 1375. The content of compound (3-1) in the obtained resin composition was 15 wt%.

[0168] Synthesis Example 3 A 500 mL four-neck flask equipped with a thermometer, a stirrer, and a condenser was charged with 25 g (0.098 mol) of bisphenol C (manufactured by Honshu Chemical Co., Ltd., product name "S-BOC"), 14.23 g (0.081 mol), potassium carbonate (0.215 mol), 1.57 g of tetrabutylammonium bromide, and 75 g of DMF. The reaction temperature was raised to 80°C, and the reaction was carried out for 4 hours. Thereafter, 5.95 g (0.039 mol) of 4-(chloromethyl)styrene (manufactured by AGC Seimi Chemical Co., Ltd., product name "CMS-14") was added, and the reaction was carried out for an additional 4 hours at 80°C. After completion of the reaction, the resulting reaction solution was diluted with 25 g of DMF, and the remaining salt was removed by filtration. The resulting solution was then poured into 250 g of methanol. The precipitated solid was filtered off, washed three times with 250 g of methanol, and then filtered off again. The obtained solid was dried in a vacuum dryer at 80°C under reduced pressure for 12 hours to obtain 23 g of a resin composition of compound (1-3) represented by formula (33) and compound (3-1) represented by formula (34). The weight-average molecular weight of compound (1-3) was 5651 and the number-average molecular weight was 2396. The content of compound (3-1) in the obtained resin composition was 6 wt%.

[0169] Synthesis Example 4 The raw materials used in Synthesis Example 3 were changed to 20 g (0.078 mol) of bisphenol C (manufactured by Honshu Chemical Co., Ltd., product name "S-BOC"), 10.93 g (0.062 mol), 25.88 g (0.187 mol) of potassium carbonate, 2.52 g of tetrabutylammonium bromide, 60 g of DMF, and 5.72 g (0.037 mol) of 4-(chloromethyl)styrene (manufactured by AGC Seimi Chemical Co., Ltd., product name "CMS-14"), and the reaction temperature was changed to 90 ° C., and synthesis was carried out in the same manner as in Synthesis Example 3, to obtain 21 g of a resin composition of compound (1-4) represented by the following formula (35) and compound (3-1) represented by the formula (34). The weight average molecular weight of compound (1-4) was 8649, and the number average molecular weight was 1577. The content of the compound (3-1) in the resulting resin composition was 11% by weight.

[0170]

[0171] Synthesis Example 5 The raw materials used in Synthesis Example 3 were changed to 25 g (0.065 mol) of 4,4'-butylidenebis-(6-t-butyl-3-methylphenol) (manufactured by Mitsubishi Chemical Corporation, product name "Yoshinox BB"), 9.15 g (0.052 mol) of m-xylene dichloride, 19.87 g (0.144 mol) of potassium carbonate, 2.10 g of tetrabutylammonium bromide, 75 g of DMF, and 4.79 g (0.048 mol) of an isomer mixture of 3-(chloromethyl)styrene and 4-(chloromethyl)styrene (manufactured by AGC Seimi Chemical Co., Ltd., product name "CMS-P"), and the reaction temperature was changed to 105 ° C., and synthesis was carried out in the same manner as above, to obtain 33 g of a resin composition of a compound (1-5) represented by the following formula (36) and a compound (3-2) represented by the following formula (37). The weight average molecular weight of the compound (1-5) was 6209, and the number average molecular weight was 3066. The content of the compound (3-2) in the resulting resin composition was 5% by weight.

[0172]

[0173]

[0174] Synthesis Example 6 The raw materials used in Synthesis Example 3 were changed to 25 g (0.065 mol) of 4,4'-butylidenebis-(6-t-butyl-3-methylphenol) (manufactured by Mitsubishi Chemical Corporation, product name "Yoshinox BB"), 10.61 g (0.061 mol) of m-xylene dichloride, 21.62 g (0.156 mol) of potassium carbonate, 2.10 g of tetrabutylammonium bromide, 75 g of DMF, and 2.78 g (0.018 mol) of an isomer mixture of 3-(chloromethyl)styrene and 4-(chloromethyl)styrene (manufactured by AGC Seimi Chemical Co., Ltd., product name "CMS-P"), and the reaction temperature was changed to 105 ° C., and synthesis was carried out in the same manner as above, to obtain 20 g of a resin composition of the compound (1-6) represented by the formula (36) and the compound (3-2) represented by the formula (37). The weight average molecular weight of the compound (1-6) was 10,390, and the number average molecular weight was 3,774. The content of the compound (3-2) in the resulting resin composition was 4% by weight.

[0175] Synthesis Example 7 The raw materials used in Synthesis Example 3 were changed to 25 g (0.065 mol) of 4,4'-butylidenebis-(6-t-butyl-3-methylphenol) (manufactured by Mitsubishi Chemical Corporation, product name "Yoshinox BB"), 10.89 g (0.062 mol) of m-xylene dichloride, 21.67 g (0.157 mol) of potassium carbonate, 2.10 g of tetrabutylammonium bromide, 75 g of DMF, and 1.42 g (0.009 mol) of an isomer mixture of 3-(chloromethyl)styrene and 4-(chloromethyl)styrene (manufactured by AGC Seimi Chemical Co., Ltd., product name "CMS-P"), and the reaction temperature was changed to 105 ° C., and synthesis was carried out in the same manner as above, to obtain 22 g of a resin composition of the compound (1-7) represented by the formula (36) and the compound (3-2) represented by the formula (37). The weight average molecular weight of the compound (1-7) was 17004, and the number average molecular weight was 6036. The content of the compound (3-2) in the resulting resin composition was 2% by weight.

[0176] Synthesis Example 8 Synthesis was performed in the same manner as in Synthesis Example 3, except that the raw materials used were changed to 20 g (0.052 mol) of 4,4'-butylidenebis-(6-t-butyl-3-methylphenol) (manufactured by Mitsubishi Chemical Corporation, product name "Yoshinox BB"), 11.41 g (0.065 mol), 21.62 g (0.156 mol) of potassium carbonate, 2.52 g of tetrabutylammonium bromide, 75 g of DMF, and 4.20 g (0.031 mol) of o-allylphenol, and the reaction temperature was changed to 105°C. 16 g of compound (1-8) represented by the following formula (38) was obtained. The weight-average molecular weight of compound (1-8) was 7255, and the number-average molecular weight was 2923. No compound corresponding to compound (3) was detected.

[0177]

[0178] Synthesis Example 9 A 500 mL four-neck flask equipped with a thermometer, a stirrer, and a condenser was charged with 25 g (0.065 mol) of 4,4'-butylidenebis-(6-t-butyl-3-methylphenol) (manufactured by Mitsubishi Chemical Corporation, product name "Yoshinox BB"), 9.15 g (0.052 mol) of m-xylene dichloride, 19.87 g (0.144 mol) of potassium carbonate, 2.10 g of tetrabutylammonium bromide, and 75 g of DMF. The reaction temperature was raised to 105°C, and the reaction was carried out for 4 hours. After removing the remaining salt by filtration, the resulting solution was added to 250 g of water. The precipitated solid was filtered off, washed three times with 250 g of water, and then filtered off again. The resulting solid was dried in a vacuum dryer at 100°C under reduced pressure for 12 hours.

[0179] The solid obtained above, 4.08 g (0.039 mol) of methacrylic acid chloride, and 75 g of dichloromethane were added to a 500 mL four-neck flask equipped with a thermometer, a stirrer, and a condenser, and dissolved by stirring at room temperature. Subsequently, 5.26 g (0.052 mol) of triethylamine was added dropwise over 15 minutes, and the reaction was carried out at room temperature for 1 hour. After completion of the reaction, the resulting reaction solution was poured into 250 g of methanol. The precipitated solid was filtered, washed three times with 250 g of methanol, and then filtered again. The resulting solid was dried in a vacuum dryer at 80°C under reduced pressure for 12 hours to obtain 20 g of a resin composition containing compound (1-9) represented by the following formula (39) and compound (3-3) represented by the following formula (40). The weight-average molecular weight of compound (1-9) was 6109, and the number-average molecular weight was 2871. The content of compound (3-3) in the resulting resin composition was 6 wt%.

[0180]

[0181]

[0182] [Synthesis Example 10] The raw materials used in Synthesis Example 3 were changed to 25 g (0.081 mol) of 2,2'-diallylbisphenol A (manufactured by Daiwa Chemical Industry Co., Ltd., product name "DABPA"), 11.75 g (0.067 mol), potassium carbonate, 24.65 g (0.178 mol), tetrabutylammonium bromide, 1.31 g, DMF, 75 g, and an isomer mixture of 3-(chloromethyl)styrene and 4-(chloromethyl)styrene (manufactured by AGC Seimi Chemical Co., Ltd., product name "CMS-P"), 4.95 g (0.032 mol), and the reaction temperature was changed to 90 ° C., and synthesis was carried out in the same manner as above. 24 g of a resin composition of a compound (1-10) represented by the following formula (41) and a compound (3-4) represented by the following formula (42) was obtained. The weight average molecular weight of the compound (1-10) was 6109, and the number average molecular weight was 2871. The content of the compound (3-4) in the resulting resin composition was 5% by weight.

[0183]

[0184]

[0185] [Synthesis Example 11] The raw materials used in Synthesis Example 3 were 4,4'-(3,3,5-trimethylcyclohexane-1,1-diyl)diphenol (manufactured by Honshu Chemical Co., Ltd., product name "BisP-HTG") 25 g (0.081 mol), m-xylene dichloride 11.82 g (0.067 mol), potassium carbonate 26.71 g (0.193 mol), tetrabutylammonium bromide 2.60 g, DMF 75 g, 3- (chloromethyl) styrene and 4- (chloromethyl) styrene isomer mixture (manufactured by AGC Seimi Chemical Co., Ltd., product name "CMS-P") 6.15 g (0.040 mol), and the reaction temperature was changed to 70 ° C. The same synthesis was performed except that a resin composition of a compound (1-11) represented by the following formula (43) and a compound (3-5) represented by the following formula (44) was obtained. The weight average molecular weight of the compound (1-11) was 6226, and the number average molecular weight was 2561. The content of the compound (3-5) in the obtained resin composition was 6% by weight.

[0186]

[0187]

[0188] [Synthesis Example 12] The raw materials used in Synthesis Example 3 were 9,9'-bis(4-hydroxy-3-methylphenyl)fluorene (manufactured by Honshu Chemical, product name "BisOC-FL") 25 g (0.066 mol), m-xylene dichloride 9.25 g (0.053 mol), potassium carbonate 21.91 g (0.159 mol), tetrabutylammonium bromide 2.13 g, DMF 75 g, 3- (chloromethyl) styrene and 4- (chloromethyl) styrene isomer mixture (manufactured by AGC Seimi Chemical Co., Ltd., product name "CMS-P") 6.05 g (0.040 mol), and the reaction temperature was changed to 90 ° C. The same synthesis was performed except that the compound (1-12) represented by the following formula (45) and the compound (3-6) represented by the following formula (46) were synthesized in the same manner to obtain 21 g of a resin composition. The weight average molecular weight of the compound (1-12) was 6288, and the number average molecular weight was 2442. The content of the compound (3-6) in the obtained resin composition was 5% by weight.

[0189]

[0190]

[0191] [Synthesis Example 13] The raw materials used in Synthesis Example 3 were replaced with 12.0 g (0.032 mol) of 9,9'-bis(4-hydroxy-3-methylphenyl)fluorene (manufactured by Honshu Chemical Co., Ltd., product name "BisOC-FL"), 12.2 g (0.048 mol) of bisphenol C (manufactured by Honshu Chemical Co., Ltd., product name "S-BOC"), 11.6 g (0.066 mol) of m-xylene dichloride, 26.29 g (0.190 mol) of potassium carbonate, and 2.5 g (0.190 mol) of tetrabutylammonium bromide. The synthesis was carried out in the same manner as above, except that the amount of styrene, styrene, and styrene were changed to 6 g, 75 g of DMF, 5.24 g (0.034 mol) of an isomer mixture of 3-(chloromethyl)styrene and 4-(chloromethyl)styrene (manufactured by AGC Seimi Chemical Co., Ltd., product name "CMS-P"), and the reaction temperature was changed to 90°C. 20 g of a resin composition of compound (1-13) represented by formula (47) below, compound (3-7) represented by formula (50) below, and compound (3-6) represented by formula (46) was obtained. The weight average molecular weight of compound (1-13) was 6288 and the number average molecular weight was 2442. The total content of compound (3-7) and compound (3-6) in the obtained resin composition was 5 wt%.

[0192]

[0193] In the above formula (46), each Ar independently represents one structure selected from the group consisting of a structure represented by the following formula (48) and a structure represented by the following formula (49): In formulas (48) and (49), the symbol "*" represents a bond.

[0194]

[0195]

[0196] Synthesis Example 14 The raw materials used in Synthesis Example 3 were replaced with 20.0 g (0.053 mol) of 9,9′-bis(4-hydroxy-3-methylphenyl)fluorene (manufactured by Honshu Chemical Industry Co., Ltd., product name “BisOC-FL”), 3.40 g (0.013 mol) of bisphenol C (manufactured by Honshu Chemical Industry Co., Ltd., product name “S-BOC”), 9.25 g (0.053 mol) of m-xylene dichloride, 21.91 g (0.190 mol) of potassium carbonate, and 2.1 g (0.190 mol) of tetrabutylammonium bromide. The synthesis was carried out in the same manner as above, except that the amount of styrene, 3 g, 75 g of DMF, and 4.84 g (0.032 mol) of an isomer mixture of 3-(chloromethyl)styrene and 4-(chloromethyl)styrene (manufactured by AGC Seimi Chemical Co., Ltd., product name "CMS-P") were changed, and the reaction temperature was changed to 90°C. 18 g of a resin composition of compound (1-14) represented by formula (47), compound (3-7) represented by formula (50), and compound (3-6) represented by formula (46) was obtained. The weight average molecular weight of compound (1-14) was 5608, and the number average molecular weight was 2649. The total content of compound (3-7) and compound (3-6) in the obtained resin composition was 4 wt%.

[0197] Synthesis Example 15 The raw materials used in Synthesis Example 3 were replaced with 21.0 g (0.055 mol) of 9,9′-bis(4-hydroxy-3-methylphenyl)fluorene (manufactured by Honshu Chemical Industry Co., Ltd., product name “BisOC-FL”), 3.56 g (0.014 mol) of bisphenol C (manufactured by Honshu Chemical Industry Co., Ltd., product name “S-BOC”), 11.0 g (0.063 mol) of m-xylene dichloride, 23.0 g (0.190 mol) of potassium carbonate, and 2.24 g (0.190 mol) of tetrabutylammonium bromide. The synthesis was carried out in the same manner as above, except that the amount of styrene, 75.0 g of DMF, and 2.89 g (0.019 mol) of an isomer mixture of 3-(chloromethyl)styrene and 4-(chloromethyl)styrene (manufactured by AGC Seimi Chemical Co., Ltd., product name "CMS-P") were changed, and the reaction temperature was changed to 90°C. 19 g of a resin composition of compound (1-15) represented by formula (47), compound (3-7) represented by formula (50), and compound (3-6) represented by formula (46) was obtained. The weight average molecular weight of compound (1-15) was 13,015, and the number average molecular weight was 4,000. In the obtained resin composition, the total content of compound (3-7) and compound (3-6) was 3 wt%.

[0198] Synthesis Example 16 The raw materials used in Synthesis Example 3 were replaced with 20.0 g (0.053 mol) of 9,9′-bis(4-hydroxy-3-methylphenyl)fluorene (manufactured by Honshu Chemical Industry Co., Ltd., product name “BisOC-FL”), 5.11 g (0.018 mol) of 4,4′-(α-methylbenzylidene)bisphenol (manufactured by Honshu Chemical Industry Co., Ltd., product name “BisP-AP”), 10.3 g (0.059 mol) of m-xylene dichloride, 23.4 g (0.169 mol) of potassium carbonate, and tetrabutyl ether. The synthesis was carried out in the same manner as above, except that the ingredients were changed to 2.27 g of ammonium bromide, 75.0 g of DMF, and 5.38 g (0.035 mol) of an isomer mixture of 3-(chloromethyl)styrene and 4-(chloromethyl)styrene (manufactured by AGC Seimi Chemical Co., Ltd., product name "CMS-P"), to obtain 24 g of a resin composition of compound (1-16) represented by formula (51) below, compound (3-6) represented by formula (46) above, and compound (3-8) represented by formula (53) below. The weight-average molecular weight of compound (1-16) was 5740 and the number-average molecular weight was 2358. The total content of compound (3-6) and compound (3-8) in the obtained resin composition was 6 wt%.

[0199]

[0200] In the above formula (50), each Ar independently represents one structure selected from the group consisting of a structure represented by the following formula (48) and a structure represented by the following formula (52): In formulas (48) and (52), the symbol "*" represents a bond.

[0201]

[0202]

[0203] Synthesis Example 17 The raw materials used in Synthesis Example 3 were replaced with 10.6 g (0.041 mol) of 4,4'-methylenebis(2,6-dimethylphenol) (manufactured by Deepak, product name "Tetramethylbisphenol F"), 5.11 g (0.018 mol) of 4,4'-bishydroxy-3,3',5,5'-tetramethylbiphenyl, 14.5 g (0.083 mol) of m-xylene dichloride, 34.2 g (0.248 mol) of potassium carbonate, and tetrabutylammonium hydroxide. The synthesis was carried out in the same manner as above, except that the ingredients were changed to 3.33 g of methyl bromide, 75.0 g of DMF, and 7.56 g (0.050 mol) of an isomer mixture of 3-(chloromethyl)styrene and 4-(chloromethyl)styrene (manufactured by AGC Seimi Chemical Co., Ltd., product name "CMS-P"), to obtain 23 g of a resin composition of compound (1-17) represented by the following formula (54), compound (3-9) represented by the following formula (57), and compound (3-10) represented by the following formula (58). The weight average molecular weight of compound (1-17) was 5740 and the number average molecular weight was 2358. The total content of compound (3-9) and compound (3-10) in the obtained resin composition was 19 wt%.

[0204]

[0205] In the above formula (54), each Ar independently represents one structure selected from the group consisting of a structure represented by the following formula (55) and a structure represented by the following formula (56): In formulas (55) and (56), the symbol "*" represents a bond.

[0206]

[0207]

[0208]

[0209] Synthesis Example 18 The raw materials used in Synthesis Example 3 were 7.28 g (0.028 mol) of 4,4′-methylenebis(2,6-dimethylphenol) (manufactured by Deepak Chemical Industry, product name “Tetramethylbisphenol F”), 18.0 g (0.043 mol) of a phenol compound represented by the following formula (59) (manufactured by Gun-ei Chemical Industry, product name “XB26H”), 9.94 g (0.057 mol) of m-xylene dichloride, 23.6 g (0.170 mol) of potassium carbonate, and tetrabutyl ether. The synthesis was carried out in the same manner as above, except that the ingredients were changed to 2.29 g of ammonium bromide, 75.0 g of DMF, and 5.20 g (0.050 mol) of an isomer mixture of 3-(chloromethyl)styrene and 4-(chloromethyl)styrene (manufactured by AGC Seimi Chemical Co., Ltd., product name "CMS-P"), to obtain 24 g of a resin composition of compound (1-18) represented by formula (60) below, compound (3-9) represented by formula (57) above, and compound (3-11) represented by formula (62) below. The weight-average molecular weight of compound (1-18) was 10,773, and the number-average molecular weight was 2,298. The total content of compound (3-9) and compound (3-11) in the obtained resin composition was 9 wt%.

[0210]

[0211]

[0212] In the above formula (58), each Ar independently represents one structure selected from the group consisting of a structure represented by the following formula (55) and a structure represented by the following formula (61): In formulas (55) and (61), the symbol "*" represents a bond.

[0213]

[0214]

[0215] [Synthesis Example 19] The raw materials used in Synthesis Example 3 were changed to 18.0 g (0.070 mol) of bisphenol C (manufactured by Honshu Chemical Co., Ltd., product name "S-BOC"), 7.50 g (0.047 mol) of 2,7-dihydroxynaphthalene, 16.39 g (0.094 mol) of m-xylene dichloride, 38.8 g (0.281 mol) of potassium carbonate, 3.77 g of tetrabutylammonium bromide, 75.0 g of DMF, and 8.57 g (0.050 mol) of an isomer mixture of 3-(chloromethyl)styrene and 4-(chloromethyl)styrene (manufactured by AGC Seimi Chemical Co., Ltd., product name "CMS-P"), and the same method was used to obtain 19 g of a resin composition of a compound (1-19) represented by the following formula (63), a compound (3-7) represented by the formula (50), and a compound (3-12) represented by the following formula (65). The weight average molecular weight of the compound (1-19) was 5482, and the number average molecular weight was 1673. In the obtained resin composition, the total content of the compound (3-7) and the compound (3-12) was 12% by weight.

[0216]

[0217] In the above formula (63), each Ar independently represents one structure selected from the group consisting of a structure represented by the following formula (49) and a structure represented by the following formula (64): In formulas (49) and (64), the symbol "*" represents a bond.

[0218]

[0219]

[0220] Synthesis Example 20 The raw materials used in Synthesis Example 3 were replaced with 20.0 g (0.052 mol) of 4,4′-butylidenebis-(6-t-butyl-3-methylphenol) (manufactured by Mitsubishi Chemical Corporation, product name “Yoshinox BB”), 4,4′,4″-(1-methylpropanyl-3-ylidene)tris(6-tert-butyl-m-cresol) (manufactured by ADEKA Corporation, product name “ADK STAB The same synthesis method was used except that the ingredients were changed to 7.12 g (0.013 mol) of m-xylene dichloride (AO-30), 9.15 g (0.052 mol), 28.8 g (0.173 mol) of potassium carbonate, 3.77 g of tetrabutylammonium bromide, 75.0 g of DMF, and 8.98 g (0.059 mol) of an isomer mixture of 3-(chloromethyl)styrene and 4-(chloromethyl)styrene (manufactured by AGC Seimi Chemical Co., Ltd., product name "CMS-P"), to obtain 18 g of a resin composition of compound (1-20) represented by formula (66) below, compound (3-2) represented by formula (37) above, and compound (3-13) represented by formula (70) below. The weight average molecular weight of compound (1-20) was 7807, and the number average molecular weight was 2311. In the resulting resin composition, the total content of the compound (3-2) and the compound (3-13) was 13% by weight.

[0221]

[0222] In the above formula (66), each Ar independently represents one structure selected from the group consisting of a structure represented by the following formula (67) and a structure represented by the following formula (68). In formula (68), Z represents a structure represented by the following formula (69), and in formula (69), Ar is the same as Ar in formula (66). In formulas (66) and (67), the symbol "*" represents a bond.

[0223]

[0224]

[0225] Synthesis Example 21 17 g of a resin composition of compound (1-21) represented by the following formula (71) and compound (3-1) represented by the formula (34) was obtained in the same manner as in Synthesis Example 1, except that 6.8 g of p-xylene dichloride was used instead of 6.8 g of m-xylene dichloride. The weight average molecular weight of compound (1-21) was 8416 and the number average molecular weight was 1203. The content of compound (3-1) in the obtained resin composition was 26 wt %.

[0226]

[0227] Synthesis Example 22 Synthesis was performed in the same manner as in Synthesis Example 3, except that the raw materials used were changed to 25.0 g (0.081 mol) of 2,5-dihydroxy(diphenyl)phosphine oxide, 11.8 g (0.067 mol) of m-xylene dichloride, 26.7 g (0.193 mol) of potassium carbonate, 2.60 g of tetrabutylammonium bromide, 75.0 g of DMF, and 6.15 g (0.040 mol) of 4-(chloromethyl)styrene (manufactured by AGC Seimi Chemical Co., Ltd., product name "CMS-14"), to obtain 17 g of a resin composition containing compound (1-22) represented by formula (72) below and compound (3-14) represented by formula (73) below. The weight-average molecular weight of compound (1-22) was 5784 and the number-average molecular weight was 2215. The content of compound (3-14) in the obtained resin composition was 5 wt %.

[0228]

[0229]

[0230] Synthesis Example 23 A 500 mL four-neck flask equipped with a thermometer, a stirrer, and a condenser was charged with 25 g (0.098 mol) of bisphenol C (manufactured by Honshu Chemical Co., Ltd., product name "S-BOC"), 14.23 g (0.081 mol) of m-xylene dichloride, 0.215 mol of potassium carbonate, 1.57 g of tetrabutylammonium bromide, and 75 g of DMF. The reaction temperature was raised to 80°C, and the reaction was carried out for 4 hours. After removing the remaining salt by filtration, the resulting solution was added to 250 g of water. The precipitated solid was filtered off, washed three times with 250 g of water, and then filtered again. The resulting solid was dried in a vacuum dryer at 100°C under reduced pressure for 12 hours, yielding 16 g of compound (1-23) represented by the following formula (74). The weight-average molecular weight was 5868, and the number-average molecular weight was 1976.

[0231]

[0232] [Examples 1 to 27, Comparative Examples 1 to 3] <Solvent Solubility> Resin compositions containing the polyether compounds produced in Synthesis Examples 1 to 23, a vinyl compound (manufactured by Mitsubishi Gas Chemical Company, Inc., product name "OPE-2st2200"), a maleimide compound (manufactured by KI Chemical Industry Co., Ltd., product name "BMI-80"), a maleimide compound (manufactured by Mitsubishi Chemical Corporation, product name "Designer Molecules, product name "BMI-3000"), an allyl compound (manufactured by Mitsubishi Chemical Corporation, product name "TAIC"), an elastomer (manufactured by Kuraray Co., Ltd., product name "Septon 8007"), an antioxidant (manufactured by ADEKA Corporation, product name "AO-60"), and dicumyl peroxide (DCP) as a curing accelerator were weighed out in the blending ratios shown in Table 1. Thereafter, toluene was added so that the solids concentration was 50% by weight, and the mixture was mixed at room temperature for 1 hour to obtain a varnish-like resin composition. The results were visually confirmed, and samples with no remaining solids were rated as toluene solubility "A," while samples with remaining solids were rated as toluene solubility "B." The results are shown in Table 1.

[0233] <Film-Forming Ability> The obtained varnish-like resin composition was applied to a separator (a silicone-treated polyethylene terephthalate film) using an applicator to form a 10 cm x 15 cm coating film, which was then dried at 130°C for 15 minutes. A cured product was then obtained by vacuum pressing at 160°C for 15 minutes and at 200°C for 2 hours. Film-formed cured products larger than 2 cm x 10 cm that could be removed were evaluated as having film-formability "A," and those that could not be removed were evaluated as having film-formability "B." The results are shown in Table 1. Comparative Example 2 was not eligible for evaluation.

[0234] <Dielectric Loss Tangent> The dielectric loss tangent at 10 GHz of the obtained cured products was measured by the method described above. The results are shown in Table 1. For Comparative Examples 2 and 3, a cured film for evaluation could not be obtained, and evaluation was not possible.

[0235] <Copper foil peel strength> A cured film with copper foil was prepared using the obtained varnish-like resin composition by the method described above. The copper foil peel strength of the obtained cured film with copper foil was measured by the method described above. The results are shown in Table 1. For Comparative Examples 2 and 3, a cured film for evaluation could not be obtained, and evaluation was not possible.

[0236]

[0237]

[0238]

[0239] [Evaluation of Results] From the results in Tables 1 to 3, it was found that the resin composition containing the polyether compound according to the present invention has excellent solvent solubility and excellent film-forming properties when cured. It was also found that the cured product of the resin composition containing the polyether compound according to the present invention has low dielectric properties even in a high-frequency environment and has excellent metal adhesion.

[0240] The resin composition according to the present invention can be applied to various fields such as adhesives, paints, civil engineering and construction materials, various composite materials including carbon fiber reinforced plastics (CFRP), and insulating materials for electric and electronic parts, and is particularly useful as insulating casting materials, laminating materials, sealing materials, etc. in the electric and electronic fields.

Claims

1. A polyether compound represented by the following formula (1): (In formula (1), l and n represent 0 or 1, m represents an integer of 1 to 50, and Ar １ each independently represents an aromatic hydrocarbon group having 6 to 100 carbon atoms and not having a structure represented by formula (2), Ar ２ represents a structure represented by formula (3) or a structure represented by formula (4) when m is 1 and n is 0, and when m is 2 to 50 or n is 1, each independently represents at least one structure selected from the group consisting of a structure represented by formula (3) and a structure represented by formula (4), and each Y independently represents a group containing an ethylenically unsaturated double bond having 3 to 50 carbon atoms. (In formulas (2) to (4), the symbol "*" represents a bond, and A １ ~A １０ are each independently any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group, and a naphthyl group, and R １ ~R ８ are each independently any one selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms.

2. The polyether compound according to claim 1, wherein Y in formula (1) contains at least one group selected from the group consisting of a 2-vinylbenzyl group, a 3-vinylbenzyl group, a 4-vinylbenzyl group, an allyl group, a methallyl group, a cinnamyl group, an acryloyl group, a methacryloyl group, a 2-allylphenyl group, a 2-propenylphenyl group, a 4-vinylphenyl group, a 4-isopropenylphenyl group, a 2-methoxy-4-allylphenyl group, and a 2-methoxy-4-propenylphenyl group.

3. Ar in the formula (1) １ is at least one group selected from the group consisting of groups represented by formulas (5) to (8). (In formulas (5) to (8), the symbol "*" represents a bond, and X ４ represents a direct bond, a divalent hydrocarbon group having 1 to 20 carbon atoms, —O—, —S—, —CO—, —C(O)—O—, —C(O)—NH—, —SO—, or —SO ２ -, -C(CF ３ ) ２ - and -P(O)-, X5 is a trivalent hydrocarbon group having 1 to 20 carbon atoms, and X ６ is a tetravalent hydrocarbon group having 1 to 20 carbon atoms, and R ９ ~R ５０ are each independently any one selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms, and Z represents a structure represented by the following formula (9): (In formula (9), the symbol "*" represents a bond, M represents an integer of 1 to 50, N represents 0 or 1, and Ar １ and Y is Ar in formula (1). １ and Y, and Ar ２ represents a structure represented by formula (3) or a structure represented by formula (4) when M is 1 and N is 0, or when M is 0 and N is 1, and represents at least one structure selected from the group consisting of a structure represented by formula (3) and a structure represented by formula (4) when M is 2 to 50, or when M is 1 and N is 1.

4. The polyether compound according to claim 1, having a weight average molecular weight in terms of polystyrene of 1,000 to 100,000.

5. A resin composition containing the polyether compound of claim 1 and a curable compound having a structure different from that of the polyether compound of claim 1.

6. The resin composition according to claim 5, wherein the curable compound is a compound represented by formula (1) where l is 1, and m and n are 0.

7. The resin composition according to claim 5, further comprising a curing accelerator.

8. The resin composition according to claim 5, wherein the curable compound has at least one substituent selected from the group consisting of an epoxy group, an ester group, an oxazine group, a cyanate group, a maleimide group, an acryloyl group, a methacryloyl group, a styryl group, an allyl group, a vinyl group, a propenyl group, and a benzoxazine group.

9. The resin composition according to claim 5, further comprising an antioxidant.

10. A cured product of the resin composition according to any one of claims 5 to 9.

11. A build-up film comprising the cured product according to claim 10.

12. A copper-clad laminate comprising the cured product of claim 10.

13. A laminate comprising the cured product according to claim 10.

14. An electric or electronic part comprising the cured product according to claim 10.

15. An electric or electronic part comprising the laminate according to claim 13.

16. Use of the resin composition according to any one of claims 5 to 9 as a raw material for electrical and electronic parts.

17. A method for producing the polyether compound according to any one of claims 1 to 4, comprising the step of reacting a phenol compound, a divalent aromatic halomethyl compound, and a monovalent ethylenically unsaturated double bond-containing compound in the presence of a basic compound.

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