Resin composition, and prepregs, resin-coated films, resin-coated metal foils, metal-clad laminates, and wiring boards using the same.

Abstract

To provide a resin composition that maintains adhesion while also possessing low dielectric properties and a high glass transition temperature (Tg) in the cured product. [Solution] A resin composition comprising a polyphenylene ether compound (A) having a carbon-carbon unsaturated double bond in its molecule, a polyfunctional vinyl aromatic copolymer (B) containing repeating units (b1) derived from a divinyl aromatic copolymer and repeating units (b2) derived from a monovinyl aromatic compound, and a nitrogen-containing compound (C) having at least one of the structural units represented by formulas (1-1), (1-2), and (1-3).

Description

Technical Field

[0001] The present invention relates to a resin composition, a prepreg using the same, a resin film, a metal foil with resin, a metal-clad laminate, and a wiring board.

Background Art

[0002] With the increase in the amount of information processing in various electronic devices, mounting technologies such as high integration of semiconductor devices mounted, high density of wirings, and multilayerization have rapidly advanced. Generally, thermosetting resins are used as substrate materials for configuring the base materials of wiring boards used in various electronic devices. For coping with high temperatures such as reflow and multilayerization, high heat resistance (glass transition temperature) is required, and low dielectric constant and dielectric tangent are required to increase the signal transmission speed and reduce the loss during signal transmission.

[0003] As such a substrate material, for example, Patent Document 1 reports a resin composition containing a modified polyphenylene ether compound and an aromatic polymer having a specific structural unit.

[0004] On the other hand, in addition to low dielectric properties, properties such as adhesiveness are also required for the base materials of wiring boards for various electronic devices. Patent Document 2 describes that by including a nitrogen-containing polymer having a specific repeating structural unit, in addition to low dielectric properties, a composition and a laminate excellent in curability and adhesiveness can be obtained.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] The resin composition containing the modified polyphenylene ether compound and aromatic polymer described in Patent Document 1 can provide a cured or molded product with low dielectric properties and high heat resistance. On the other hand, it is common practice to include inorganic fillers in curable resin compositions to improve the heat resistance and flame retardancy of the cured product. However, it has become clear that resin compositions containing polyfunctional vinyl aromatic copolymers, as shown in the aforementioned document, may have poor adhesion when inorganic fillers are added.

[0007] Furthermore, while the resin composition containing the nitrogen-containing polymer described in Patent Document 2 exhibits excellent adhesion and curability, it suffers from a somewhat high dielectric loss tangent (Df) and a low glass transition temperature (Tg).

[0008] The present invention has been made in view of these circumstances, and aims to provide a resin composition that maintains adhesion while also possessing low dielectric properties and a high glass transition temperature (Tg) in the cured product. Furthermore, it aims to provide a prepreg, a resin-coated film, a resin-coated metal foil, a metal-clad laminate, and a wiring board using the resin composition. [Means for solving the problem]

[0009] A resin composition according to one aspect of the present invention is characterized by comprising a polyphenylene ether compound (A) having a carbon-carbon unsaturated double bond in its molecule, a polyfunctional vinyl aromatic copolymer (B) containing repeating units (b1) derived from a divinyl aromatic copolymer and repeating units (b2) derived from a monovinyl aromatic compound, and a nitrogen-containing compound (C) having at least one of the structural units represented by the following formulas (1-1), (1-2), and (1-3).

[0010] [ka] [In formulas (1-1) to (1-3), R 1Each of these is independently a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a nitro group, a cyano group, a primary to tertiary amino group, or a salt of a primary to tertiary amino group. Each of these is independently an integer from 0 to 2. When n is 2, multiple R 1 These elements may be identical or different, and may be joined in any combination to form part of a ring structure. [Effects of the Invention]

[0011] According to the present invention, it is possible to provide a resin composition that maintains adhesion while also possessing low dielectric properties and a high glass transition temperature (Tg) in the cured product. Furthermore, by using the resin composition, it is possible to provide prepregs, resin-coated films, resin-coated metal foils, metal-clad laminates, and wiring boards with excellent properties. [Brief explanation of the drawing]

[0012] [Figure 1] Figure 1 is a schematic cross-sectional view showing the configuration of a prepreg according to one embodiment of the present invention. [Figure 2] Figure 2 is a schematic cross-sectional view showing the configuration of a metal-clad laminate according to one embodiment of the present invention. [Figure 3] Figure 3 is a schematic cross-sectional view showing the configuration of a wiring board according to one embodiment of the present invention. [Figure 4] Figure 4 is a schematic cross-sectional view showing the structure of a resin-coated metal foil according to one embodiment of the present invention. [Figure 5] Figure 5 is a schematic cross-sectional view showing the structure of a resin-coated film according to one embodiment of the present invention. [Modes for carrying out the invention]

[0013] (Resin composition) A resin composition according to an embodiment of the present invention (hereinafter also simply referred to as "resin composition") comprises a polyphenylene ether compound (A) having a carbon-carbon unsaturated double bond in its molecule, a polyfunctional vinyl aromatic copolymer (B) containing repeating units (b1) derived from a divinyl aromatic copolymer and repeating units (b2) derived from a monovinyl aromatic compound, and a nitrogen-containing compound (C). The nitrogen-containing compound (C) has at least one of the structural units represented by the following formulas (1-1), (1-2), and (1-3).

[0014] [ka] In formulas (1-1) to (1-3), R 1 Each of these is independently a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a nitro group, a cyano group, a primary to tertiary amino group, or a salt of a primary to tertiary amino group. Each of these is independently an integer from 0 to 2. When n is 2, multiple R 1 These elements may be identical or different, and may be joined in any combination to form part of a ring structure.

[0015] The resin composition of this embodiment contains a polyphenylene ether compound (A) and a polyfunctional vinyl aromatic copolymer (B), thereby enabling the cured product of the resin composition to possess extremely excellent low dielectric properties and a high Tg. Furthermore, by including a nitrogen-containing compound (C), the resin composition of this embodiment also exhibits excellent adhesion (particularly to copper foil).

[0016] The components of the resin composition according to this embodiment will be described in detail below.

[0017] <Polyphenylene ether compound (A)> The polyphenylene ether compound that can be used in this embodiment is not particularly limited as long as it is a polyphenylene ether compound that contains a carbon-carbon unsaturated double bond in its molecule. Specifically, it is preferable that the polyphenylene ether compound has a functional group containing a carbon-carbon unsaturated double bond. For example, a polyphenylene ether compound having at least one of the groups represented by the following formulas (4) and (5) is an example, i.e., a modified polyphenylene ether compound in which the molecular ends are substituted with at least one of the groups represented by the following formulas (4) and (5). It is believed that by including such a modified polyphenylene ether compound, a resin composition can be obtained in which a cured product with low dielectric properties and high heat resistance can be obtained.

[0018] [ka]

[0019] In equation (4), s represents an integer from 0 to 10. Also, Z represents an arylene group. Also, R9~R 11 They are independent of each other. That is, R9~R 11 These may be the same group or different groups. Also, R9~R 11 This represents a hydrogen atom or an alkyl group.

[0020] In equation (4), if s is 0, it indicates that Z is directly bonded to the end of the polyphenylene ether.

[0021] The arylene group Z described above is not particularly limited. Examples of this arylene group include monocyclic aromatic groups such as phenylene groups, and polycyclic aromatic groups in which the aromatic element is not monocyclic but polycyclic, such as naphthalene rings. Furthermore, this arylene group also includes derivatives in which the hydrogen atom bonded to the aromatic ring is substituted with a functional group such as an alkenyl group, alkynyl group, formyl group, alkylcarbonyl group, alkenylcarbonyl group, or alkynylcarbonyl group. The alkyl group is not particularly limited, for example, alkyl groups having 1 to 18 carbon atoms are preferred, and alkyl groups having 1 to 10 carbon atoms are more preferred. Specifically, examples include methyl groups, ethyl groups, propyl groups, hexyl groups, and decyl groups.

[0022] [ka]

[0023] In formula (5), R 12 This represents a hydrogen atom or an alkyl group. The alkyl group is not particularly limited, but for example, alkyl groups having 1 to 18 carbon atoms are preferred, and alkyl groups having 1 to 10 carbon atoms are more preferred. Specifically, examples include methyl groups, ethyl groups, propyl groups, hexyl groups, and decyl groups.

[0024] Preferred specific examples of substituents represented by formula (4) include, for example, substituents containing a vinylbenzyl group. Examples of substituents containing a vinylbenzyl group include substituents represented by the following formula (6). Examples of substituents represented by formula (5) include acrylate groups and methacrylate groups.

[0025] [ka]

[0026] More specifically, examples of the substituent include vinylbenzyl groups (ethenylbenzyl groups) such as p-ethenylbenzyl group and m-ethenylbenzyl group, vinylphenyl group, acrylate group, and methacrylate group.

[0027] The polyphenylene ether compound (A) has a polyphenylene ether chain in the molecule, and preferably has a repeating unit represented by the following formula (7) in the molecule.

[0028]

Chemical formula

[0029] In formula (7), t represents 1 to 50. Also, R 13 ~R 16 are each independent. That is, R 13 ~R 16 may be the same group or different groups. Also, R 13 ~R 16 represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group. Among these, a hydrogen atom and an alkyl group are preferred.

[0030] R 13 ~R 16 Specific examples of each functional group listed above are as follows.

[0031] The alkyl group is not particularly limited, but for example, an alkyl group having 1 to 18 carbon atoms is preferred, and an alkyl group having 1 to 10 carbon atoms is more preferred. Specifically, examples include methyl group, ethyl group, propyl group, hexyl group, and decyl group.

[0032] The alkenyl group is not particularly limited, but for example, an alkenyl group having 2 to 18 carbon atoms is preferred, and an alkenyl group having 2 to 10 carbon atoms is more preferred. Specifically, examples include vinyl group, allyl group, and 3-butenyl group.

[0033] The alkynyl group is not particularly limited, but for example, an alkynyl group having 2 to 18 carbon atoms is preferred, and an alkynyl group having 2 to 10 carbon atoms is more preferred. Specifically, examples include the ethynyl group and the propa-2-in-1-yl group (propargyl group).

[0034] The alkylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkyl group, but for example, alkylcarbonyl groups having 2 to 18 carbon atoms are preferred, and alkylcarbonyl groups having 2 to 10 carbon atoms are more preferred. Specifically, examples include acetyl group, propionyl group, butyryl group, isobutyryl group, pivaloyl group, hexanoyl group, octanoyl group, and cyclohexylcarbonyl group.

[0035] The alkenylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkenyl group, but for example, an alkenylcarbonyl group having 3 to 18 carbon atoms is preferred, and an alkenylcarbonyl group having 3 to 10 carbon atoms is more preferred. Specifically, examples include acryloyl groups, methacryloyl groups, and crotonoyl groups.

[0036] The alkynylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkynyl group, but for example, an alkynylcarbonyl group having 3 to 18 carbon atoms is preferred, and an alkynylcarbonyl group having 3 to 10 carbon atoms is more preferred. Specifically, for example, a propioloyl group can be mentioned.

[0037] The weight-average molecular weight (Mw) of the polyphenylene ether compound (A) is not particularly limited. Specifically, it is preferably 500 to 5000, more preferably 800 to 4000, and even more preferably 1000 to 3000. Here, the weight-average molecular weight can be measured by any general molecular weight measurement method, specifically, values ​​measured using gel permeation chromatography (GPC). Furthermore, if the polyphenylene ether compound has repeating units represented by formula (7) in its molecule, it is preferable that t is a value such that the weight-average molecular weight of the polyphenylene ether compound falls within this range. Specifically, it is preferable that t is 1 to 50.

[0038] When the weight-average molecular weight of the polyphenylene ether compound (A) is within this range, it is believed that the cured product will not only possess the excellent low dielectric properties of polyphenylene ether, resulting in superior heat resistance, but also excellent moldability. This is thought to be due to the following: In ordinary polyphenylene ethers, when the weight-average molecular weight is within this range, the molecular weight is relatively low, so the heat resistance of the cured product tends to decrease. In this respect, the polyphenylene ether compound according to this embodiment has one or more unsaturated double bonds in its molecule, so it is believed that a cured product with sufficiently high heat resistance can be obtained. Furthermore, when the weight-average molecular weight of the polyphenylene ether compound is within this range, the molecular weight is relatively low, so it is believed to have excellent moldability. Therefore, it is believed that such a polyphenylene ether compound can be obtained that not only possesses superior heat resistance, but also excellent moldability.

[0039] In polyphenylene ether compound (A), the average number of substituents (number of terminal functional groups) at the molecular ends per molecule of polyphenylene ether compound is not particularly limited. Specifically, it is preferably 1 to 3, and more preferably 1.5 to 3. If the number of terminal functional groups is too small, it tends to be difficult to obtain a cured product with sufficient heat resistance. On the other hand, if the number of terminal functional groups is too large, the reactivity becomes too high, which may lead to problems such as a decrease in the shelf life of the resin composition or a decrease in the fluidity of the resin composition. In other words, if such a polyphenylene ether compound is used, molding defects such as voids occurring during multilayer molding may occur due to insufficient fluidity, which may lead to problems with moldability, making it difficult to obtain a highly reliable printed circuit board. Therefore, it is preferable that the polyphenylene ether compound (A) of this embodiment contains polyphenylene ether compound (A-1) having 1 to 3 of the aforementioned functional groups in the molecule.

[0040] The number of terminal functional groups in polyphenylene ether compound (A) can be expressed as a numerical value representing the average number of substituents per molecule of the modified polyphenylene ether compound present in 1 mole of the polyphenylene ether compound. This number of terminal functional groups can be measured, for example, by measuring the number of hydroxyl groups remaining in the obtained modified polyphenylene ether compound and calculating the decrease from the number of hydroxyl groups in the polyphenylene ether before modification. This decrease from the number of hydroxyl groups in the polyphenylene ether before modification is the number of terminal functional groups. The number of hydroxyl groups remaining in the modified polyphenylene ether compound can be measured by adding a quaternary ammonium salt (tetraethylammonium hydroxide) that associates with hydroxyl groups to a solution of the modified polyphenylene ether compound and measuring the UV absorbance of the mixed solution.

[0041] Examples of the polyphenylene ether compound (A) in this embodiment include a modified polyphenylene ether compound represented by the following formula (8) and a modified polyphenylene ether compound represented by the following formula (9). Furthermore, these modified polyphenylene ether compounds may be used individually as the polyphenylene ether compound (A) in this embodiment, or these two modified polyphenylene ether compounds may be used in combination.

[0042] [ka]

[0043] [ka]

[0044] In equations (8) and (9), R 17 ~R 24 R 25 ~R 32 Each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group. Among these, hydrogen atoms and alkyl groups are preferred. Each independently represents a substituent having a carbon-carbon unsaturated double bond. A and B represent repeating units represented by the following formulas (10) and (11), respectively. In formula (9), Y1 represents a linear, branched, or cyclic hydrocarbon having 20 or fewer carbon atoms.

[0045] [ka]

[0046] [ka]

[0047] In equations (10) and (11), m and n represent values ​​from 0 to 20, respectively. 33 ~R36 R 37 ~R 40 Each of these independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group. Among these, hydrogen atoms and alkyl groups are preferred.

[0048] In equations (10) and (11), it is preferable that m and n represent values ​​between 0 and 20, as described above. Furthermore, it is preferable that m and n represent values ​​such that the sum of m and n is between 1 and 30. Therefore, it is more preferable that m represents values ​​between 0 and 20, n represents values ​​between 0 and 20, and the sum of m and n is between 1 and 30.

[0049] In formula (9) above, Y1 is a linear, branched, or cyclic hydrocarbon having 20 or fewer carbon atoms, as described above. Examples of Y1 include the group represented by the following formula (12).

[0050] [ka]

[0051] In the above equation (12), R 41 and R 42 Each of these independently represents either a hydrogen atom or an alkyl group. Examples of the alkyl group include a methyl group. Examples of the group represented by formula (12) include a methylene group, a methylmethylene group, and a dimethylmethylene group, among which the dimethylmethylene group is preferred.

[0052] In formulas (8) and (9), X1 and X2 are each independently substituents (functional groups) having a carbon-carbon unsaturated double bond. The substituents X1 and X2 are not particularly limited as long as they have a carbon-carbon unsaturated double bond. Examples of substituents X1 and X2 include the substituent represented by formula (4) and the substituent represented by formula (5). In the modified polyphenylene ether compound represented by formula (8) and the modified polyphenylene ether compound represented by formula (9), X1 and X2 may be the same substituent or different substituents.

[0053] More specific examples of the modified polyphenylene ether compound represented by formula (8) include, for example, the modified polyphenylene ether compound represented by the following formula (13).

[0054] [ka]

[0055] More specific examples of the modified polyphenylene ether compound represented by formula (9) include, for example, the modified polyphenylene ether compound represented by formula (14) below, and the modified polyphenylene ether compound represented by formula (15) below.

[0056] [ka]

[0057] [ka]

[0058] In equations (13) to (15) above, m and n are the same as m and n in equations (10) and (11) above. Also, in equations (13) and (14) above, R9 to R 11 s and Z are, respectively, R9 to R in equation (4) above. 11, is the same as s and Z. Also, in equations (14) and (15) above, Y1 is the same as Y1 in equation (9) above. Also, in equation (15) above, R 12 This is R in equation (5) above. 12 It is the same as this.

[0059] By using the modified polyphenylene ether compounds described above, it is possible to improve adhesion while maintaining low dielectric properties such as low dielectric loss tangent and excellent heat resistance.

[0060] Furthermore, modified polyphenylene ether compounds can be used individually or in combination of two or more types.

[0061] The polyphenylene ether compound used in the resin composition of this embodiment can be synthesized by known methods or a commercially available product can be used. Examples of commercially available products include "OPE-2st 1200" and "OPE-2st 2200" from Mitsubishi Gas Chemical Company, Inc., and "SA9000" from SABIC Innovative Plastics Corporation.

[0062] The content of polyphenylene ether compound (A) is preferably 5% to 40% by mass, and more preferably 10% to 30% by mass, based on the total amount of polyphenylene ether compound (A), polyfunctional vinyl aromatic copolymer (B), and nitrogen-containing compound (C). By including polyphenylene ether compound (A) in such a content, the resin composition of this embodiment can more reliably obtain high Tg and low dielectric properties in its cured product.

[0063] <Polyfunctional vinyl aromatic copolymer (B)> The polyfunctional vinyl aromatic copolymer (B) of this embodiment is not particularly limited as long as it is a polyfunctional vinyl aromatic copolymer containing repeating units (b1) derived from a divinyl aromatic compound. Preferably, the polyfunctional vinyl aromatic copolymer (B) contains repeating units (b1) derived from the divinyl aromatic compound and repeating units (b2) derived from a monovinyl aromatic compound. More specifically, for example, the polyfunctional vinyl aromatic polymer (A) used in the resin composition of this embodiment has repeating units (b1) derived from a divinyl aromatic compound and repeating units (b2) derived from a monovinyl aromatic compound, and when the total of repeating units (b1) and repeating units (b2) is 100 mol%, it contains repeating units (b1) in an amount of 2 mol% or more and less than 95 mol%, and repeating units (b2) in an amount of 5 mol% or more and less than 98 mol%.

[0064] The polyfunctional vinyl aromatic copolymer (B) preferably further contains a repeating unit (b1-1) represented by the following formula (16) as part of the repeating unit (b1) derived from the divinyl aromatic compound.

[0065] [ka] In formula (16), R 44 This represents an aromatic hydrocarbon group with 6 to 30 carbon atoms.

[0066] The polyfunctional vinyl aromatic copolymer (B) is defined by the following formula (17): The mole fraction of repeating unit (b1-1) in relation to the total number of repeating units (b1) and repeating units (b2) is: 0.02≦(b1-1) / [(b1)+(b1)]≦0.8 (17) A soluble polyfunctional vinyl aromatic copolymer that satisfies the above conditions, has a number-average molecular weight of 300 to 100,000, a molecular weight distribution expressed as the ratio of weight-average molecular weight to number-average molecular weight of 100.0 or less, and is soluble in toluene, xylene, tetrahydrofuran, dichloroethane, or chloroform is a preferred example. The soluble polyfunctional vinyl aromatic copolymer will also be simply referred to as a copolymer below.

[0067] The soluble polyfunctional vinyl aromatic copolymer contains, when the total of repeating units (b1) and (b2) is 100 mol%, 2 mol% or more and less than 95 mol% of repeating unit (b1), and 5 mol% or more and less than 98 mol% of repeating unit (b2). Preferably, when the total of repeating units (b1) and (b2) is 100 mol%, it contains 2 to 80 mol% of repeating unit (b1-1).

[0068] The soluble polyfunctional vinyl aromatic copolymer preferably has a number-average molecular weight Mn of 300 to 100,000, and a molecular weight distribution expressed as the ratio of weight-average molecular weight Mw to number-average molecular weight Mn (Mw / Mn) of 100.0 or less. It is also preferably soluble in toluene, xylene, tetrahydrofuran, dichloroethane, or chloroform.

[0069] The soluble polyfunctional vinyl aromatic copolymer is not limited to, but examples include copolymers containing structural units derived from repeating units (b2) derived from the monovinyl aromatic compound represented by formula (18) and repeating units (b1) derived from the divinyl aromatic compound, etc., represented by formulas (19) and (20). These structural units may be arranged regularly or randomly. [ka] [ka] [ka]

[0070] In equation (18) above, R 44 R represents an aromatic hydrocarbon group having 6 to 30 carbon atoms derived from the monovinyl aromatic compound, and in formulas (19) and (20), 45represents an aromatic hydrocarbon group having 6 to 30 carbon atoms derived from the divinyl aromatic compound, and in formulas (18) to (20), h to k each independently represent an integer from 0 to 200, provided that their sum is from 2 to 20,000.

[0071] Suitable soluble polyfunctional vinyl aromatic copolymers include, for example, R in formulas (18) to (20). 44 and R 45 However, examples include copolymers consisting of repeating units which are aromatic hydrocarbon groups selected from the group consisting of optionally substituted phenyl groups, optionally substituted biphenyl groups, optionally substituted naphthalene groups, and optionally substituted terphenyl groups.

[0072] The soluble polyfunctional vinyl aromatic copolymer is preferably solvent-soluble. Furthermore, the repeating units as used herein are derived from monomers and include units that are present in the main chain of the copolymer and appear repeatedly, as well as units or end groups present at the ends or in the side chains. Repeating units are also called structural units. In addition to those derived from the monomers mentioned above, the end groups as used herein also include end groups derived from the chain transfer agents described later.

[0073] Structural units (b1) derived from divinyl aromatic compounds are present in amounts of 2 mol% or more and less than 95 mol% of the total amount of structural units (b2) derived from divinyl aromatic compounds and monovinyl aromatic compounds. Structural units (b1) derived from divinyl aromatic compounds can take on multiple structures, such as when only one vinyl group reacts or when two vinyl groups react. Of these, it is preferable that the repeating unit in which only one vinyl group represented by the above formula (b1-1) reacts is present in amounts of 2 to 80 mol%, more preferably 5 to 70 mol%, even more preferably 10 to 60%, and particularly preferably 15 to 50% of the total amount. It is believed that setting the amount to 2 to 80 mol% results in a low dielectric loss tangent, high toughness, excellent heat resistance, and excellent compatibility with other resins. When the repeating unit (b1-1) in which only one vinyl group represented by the above formula (16) reacts is less than 2 mol% of the total amount, the heat resistance tends to decrease, and when it exceeds 80 mol%, the interlayer peel strength when formed into a laminate tends to decrease.

[0074] The soluble polyfunctional vinyl aromatic copolymer contains structural units (b2) derived from the monovinyl aromatic compound in an amount of 5 mol% or more and less than 98 mol% of the total amount. More preferably, it contains 10 mol% or more and less than 90 mol%. Even more preferably, it contains 15 mol% or more and less than 85 mol%. If the amount of structural units (b2) derived from the monovinyl aromatic compound is less than 5 mol% of the total amount, the moldability may be insufficient, and if it exceeds 98 mol%, the heat resistance of the cured product may be insufficient.

[0075] The vinyl group present in formula (16) above acts as a crosslinking component and contributes to the heat resistance of the soluble polyfunctional vinyl aromatic copolymer. On the other hand, structural unit (b2) derived from the monovinyl aromatic compound is thought to polymerize via a 1,2 addition reaction of vinyl groups, and therefore does not contain vinyl groups. In other words, structural unit (b2) derived from the monovinyl aromatic compound does not act as a crosslinking component, but contributes to the development of moldability.

[0076] Styrene is a preferred example of the monovinyl aromatic compound. Other monovinyl aromatic compounds can also be used in conjunction with styrene. In this case, when the total content of structural units derived from styrene (b2-1) and structural units derived from other monovinyl aromatic compounds (b2-2) is 100 mol%, the content of structural units derived from styrene (b2-1) is preferably 99 to 20 mol%, more preferably 98 to 30 mol%. A content of (b2-1) within this range is preferable because it provides both heat resistance to oxidative degradation and moldability. If the content of structural units (b2-1) is greater than 99 mol%, heat resistance tends to decrease, and if the content of structural units (b2-2) is greater than 80 mol%, moldability tends to decrease.

[0077] The number-average molecular weight (number-average molecular weight in terms of standard polystyrene measured using GPC) of the soluble polyfunctional vinyl aromatic copolymer is preferably 300 to 100,000, more preferably 400 to 50,000, and even more preferably 500 to 10,000. If Mn is less than 300, the amount of monofunctional copolymer components contained in the soluble polyfunctional vinyl aromatic copolymer increases, which tends to reduce the heat resistance of the cured product. If Mn exceeds 100,000, gel formation becomes easier, and the viscosity increases, which tends to reduce moldability.

[0078] The molecular weight distribution (Mw / Mn) of the soluble polyfunctional vinyl aromatic copolymer, expressed as the ratio of weight-average molecular weight (weight-average molecular weight on a standard polystyrene basis measured using GPC) to Mn, is 100.0 or less, preferably 50.0 or less, more preferably 1.5 to 30.0, and most preferably 2.0 to 20.0. When Mw / Mn exceeds 100.0, the processing characteristics of the soluble polyfunctional vinyl aromatic copolymer tend to deteriorate, and gel formation tends to occur.

[0079] The soluble polyfunctional vinyl aromatic copolymer is soluble in toluene, xylene, tetrahydrofuran, dichloroethane, or chloroform as a solvent, and is preferably soluble in any of the above solvents. In order to be a solvent-soluble and polyfunctional copolymer, it is necessary that some of the vinyl groups of divinylbenzene remain uncrosslinked and that there is an appropriate degree of crosslinking. Here, "solubility in a solvent" means that 5 g or more of the soluble polyfunctional vinyl aromatic copolymer dissolves in 100 g of the solvent, preferably 30 g or more, and more preferably 50 g or more.

[0080] The divinyl aromatic compound plays a role in forming a branched structure and making it polyfunctional, and also acts as a crosslinking component to exhibit heat resistance when the resulting soluble polyfunctional vinyl aromatic copolymer is thermoset. Examples of divinyl aromatic compounds are not limited to aromatic compounds having two vinyl groups, but divinylbenzene (including each positional isomer or mixtures thereof), divinylnaphthalene (including each positional isomer or mixtures thereof), and divinylbiphenyl (including each positional isomer or mixtures thereof) are preferably used. These can be used individually or in combination of two or more. From the viewpoint of moldability, divinylbenzene (m-isomer, p-isomer, or mixtures of their positional isomers) is more preferred.

[0081] Examples of the aforementioned monovinyl aromatic compounds include styrene and monovinyl aromatic compounds other than styrene. However, it is desirable to use styrene as an essential component and to use other monovinyl aromatic compounds in combination.

[0082] Styrene, as a monomer component, plays a role in imparting low dielectric properties and heat-resistant oxidative degradation to the soluble polyfunctional vinyl aromatic copolymer, and as a chain transfer agent, it plays a role in controlling the molecular weight of the soluble polyfunctional vinyl aromatic copolymer. In addition, monovinyl aromatic compounds other than styrene improve the solvent solubility and processability of the soluble polyfunctional vinyl aromatic copolymer.

[0083] Examples of monovinyl aromatic compounds other than styrene include vinyl aromatic compounds other than styrene that have one vinyl group, such as vinylnaphthalene and vinylbiphenyl; and nuclear alkyl-substituted vinyl aromatic compounds such as o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o-ethylvinylbenzene, m-ethylvinylbenzene, and p-ethylvinylbenzene. Preferably, ethylvinylbenzene (including each positional isomer or mixtures thereof), ethylvinylbiphenyl (including each positional isomer or mixtures thereof), or ethylvinylnaphthalene (including each positional isomer or mixtures thereof) are used because they prevent gelation of soluble polyfunctional vinyl aromatic copolymers, have a high effect in improving solvent solubility and processability, are low in cost, and are readily available. More preferably, from the viewpoint of dielectric properties and cost, ethylvinylbenzene (m-isomer, p-isomer, or mixtures of their positional isomers) is used.

[0084] Furthermore, within the limits that do not impair the effects of the present invention, in addition to divinyl aromatic compounds and monovinyl aromatic compounds, one or more other monomer components such as trivinyl aromatic compounds, trivinyl aliphatic compounds, divinyl aliphatic compounds, and monovinyl aliphatic compounds may be used, and structural units (c) derived therefrom may be introduced into the soluble polyfunctional vinyl aromatic copolymer.

[0085] Other monomer components mentioned above include, for example, 1,3,5-trivinylbenzene, 1,3,5-trivinylnaphthalene, 1,2,4-trivinylcyclohexane, ethylene glycol diacrylate, butadiene, 1,4-butanediol divinyl ether, cyclohexanedimethanol divinyl ether, diethylene glycol divinyl ether, triallyl isocyanurate, and the like. These can be used individually or in combination of two or more.

[0086] The other monomer components preferably have a mole fraction of less than 30 mol% of the total amount of all monomer components. In other words, the repeating unit (c) derived from the other monomer components preferably has a mole fraction of less than 30 mol% of the total amount of structural units (b1), (b2), and (c) derived from all monomer components constituting the copolymer.

[0087] The soluble polyfunctional vinyl aromatic copolymer is obtained by polymerizing monomers containing the divinyl aromatic compound and the monovinyl aromatic compound in the presence of a Lewis acid catalyst. Furthermore, known chain transfer agents (CTRs) may be added during polymerization to control the molecular weight.

[0088] The content of the polyfunctional vinyl aromatic copolymer (B) is preferably 40% to 80% by mass, and more preferably 50% to 70% by mass, based on the total amount of the polyphenylene ether compound (A), the polyfunctional vinyl aromatic copolymer (B), and the nitrogen-containing compound (C). By including the polyfunctional vinyl aromatic copolymer (B) in such a content, the resin composition of this embodiment can more reliably obtain excellent low dielectric properties in its cured product.

[0089] <Nitrogen-containing compounds (C)> The nitrogen-containing compound (C) used in this embodiment is a nitrogen-containing compound having at least one of the structural units represented by the following formulas (1-1), (1-2), and (1-3). Specifically, the nitrogen-containing compound (C) includes a polymer (hereinafter also referred to as "specific polymer") having at least one of the structural units represented by the following formulas (1-1), (1-2), and (1-3). [ka] In formulas (1-1) to (1-3), R 1Each of these is independently a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a nitro group, a cyano group, a primary to tertiary amino group, or a salt of a primary to tertiary amino group. Each of these is independently an integer from 0 to 2. When n is 2, multiple R 1 These elements may be identical or different, and may be joined in any combination to form part of a ring structure.

[0090] In this specification, unless otherwise specified, "hydrocarbon group" includes linear hydrocarbon groups and cyclic hydrocarbon groups. This "hydrocarbon group" may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group. "Linear hydrocarbon group" refers to a hydrocarbon group that does not contain a cyclic structure and consists only of a linear structure, and includes both linear hydrocarbon groups and branched hydrocarbon groups. "Cyclic hydrocarbon group" refers to a hydrocarbon group that contains a cyclic structure, and includes both alicyclic hydrocarbon groups and aromatic hydrocarbon groups. "Alicyclic hydrocarbon group" refers to a hydrocarbon group that contains only an alicyclic structure as its cyclic structure and does not contain an aromatic ring structure, and includes both monocyclic alicyclic hydrocarbon groups and polycyclic alicyclic hydrocarbon groups. However, it is not necessary to consist only of an alicyclic structure, and it may contain a linear structure as part of it. "Aromatic hydrocarbon group" refers to a hydrocarbon group that contains an aromatic ring structure as its cyclic structure, and includes both monocyclic aromatic hydrocarbon groups and polycyclic aromatic hydrocarbon groups. However, it is not necessary to consist only of an aromatic ring structure, and it may contain a linear structure or an alicyclic structure as part of it. "Ring member number" refers to the number of atoms that make up a ring structure, and in the case of polycyclic structures, it refers to the number of atoms that make up this polycyclic structure.

[0091] R 1 Examples of halogen atoms represented by this formula include fluorine, chlorine, bromine, and iodine atoms.

[0092] R 1 Examples of monovalent hydrocarbon groups having 1 to 20 carbon atoms, represented by [the formula], include monovalent linear hydrocarbon groups, monovalent alicyclic hydrocarbon groups, and monovalent aromatic hydrocarbon groups.

[0093] Examples of the monovalent chain hydrocarbon group include alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, and n-pentyl groups; alkenyl groups such as ethenyl, propenyl, butenyl, and pentenyl groups; and alkynyl groups such as ethynyl, propynyl, butynyl, and pentynyl groups.

[0094] Examples of the monovalent alicyclic hydrocarbon group include monocyclic cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl; polycyclic cycloalkyl groups such as norbornyl and adamantyl; monocyclic cycloalkenyl groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl; and polycyclic cycloalkenyl groups such as norborneyl.

[0095] Examples of the monovalent aromatic hydrocarbon group include aryl groups such as phenyl, tolyl, xylyl, naphthyl, and anthyl groups; and aralkyl groups such as benzyl, phenethyl, phenylpropyl, and naphthylmethyl groups.

[0096] R 1 Examples of monovalent halogenated hydrocarbon groups having 1 to 20 carbon atoms represented by the above R 1 Examples of groups represented by this symbol include monovalent hydrocarbon groups having 1 to 20 carbon atoms, in which some or all of the hydrogen atoms are replaced with halogen atoms such as fluorine, chlorine, bromine, or iodine.

[0097] R 1 The substituents on the secondary and tertiary amino groups represented by are not particularly limited, but for example, the above R 1 Examples of groups represented by include monovalent hydrocarbon groups having 1 to 20 carbon atoms. 1 The cation constituting the cation moiety in the salt of primary to tertiary amino groups represented by is not particularly limited, Na + These can be known cations such as the following.

[0098] R1 From the viewpoint of improving the polymerization reactivity and solubility of the monomer, halogen atoms, monovalent hydrocarbon groups having 1 to 6 carbon atoms, monovalent halogenated hydrocarbon groups having 1 to 6 carbon atoms, nitro groups, cyano groups, primary to tertiary amino groups, or salts of primary to tertiary amino groups are preferred, and fluorine atoms, chlorine atoms, methyl groups, nitro groups, cyano groups, t-butyl groups, phenyl groups, and amino groups are more preferred. From a similar viewpoint, n is preferably 0 or 1, and more preferably 0.

[0099] The position of one bond in the repeating unit relative to the other bond is not particularly limited, but the meta position is preferred in order to improve the polymerization reactivity of the monomer that gives the repeating unit. Furthermore, as the repeating unit, the structural unit represented by the above formula (1-2) having a pyrimidine skeleton is preferred from the viewpoint of improving the polymerization reactivity of the monomer and improving solubility in various organic solvents.

[0100] In a more preferred embodiment, the nitrogen-containing compound (C) of this embodiment has at least one of the structural units represented by the following formulas (2-1), (2-2), and (2-3). [ka] In formulas (2-1) to (2-3), R 1 And n is R in the above equations (1-1) to (1-3). 1 And is the same as n. A 1 and A 2 These are, independently, -O-, -S-, or -N(R 2 )- is. R 2 X is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms. X is a divalent organic group.

[0101] R 2 R is a hydrogen atom, or a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms. 2 Examples of monovalent hydrocarbon groups having 1 to 20 carbon atoms represented by the above R 1Examples of groups represented by include monovalent hydrocarbon groups having 1 to 20 carbon atoms. 2 In this case, some or all of the hydrogen atoms of the hydrocarbon group may be substituted with ester groups or sulfonyl groups.

[0102] R 2 From the viewpoint of improving the polymerization reactivity of the monomer, hydrogen atoms or monovalent hydrocarbon groups having 1 to 10 carbon atoms are preferred. Also, A 1 and A 2 Both are -N(R 2 )- If the two R 2 They may be the same or they may be different.

[0103] The position of one bond in the repeating unit relative to the other bond is not particularly limited, but the meta position is preferred in order to improve the polymerization reactivity of the monomer that gives the repeating unit. Furthermore, from the viewpoint of improving the polymerization reactivity of the monomer and improving solubility in various organic solvents, the repeating unit represented by the above general formula (2-2) having a pyrimidine skeleton is preferred.

[0104] Examples of monomers that provide such repeating units include 4,6-dichloropyrimidine, 4,6-dibromopyrimidine, 2,4-dichloropyrimidine, 2,5-dichloropyrimidine, 2,5-dibromopyrimidine, 5-bromo-2-chloropyrimidine, 5-bromo-2-fluoropyrimidine, 5-bromo-2-iodopyrimidine, 2-chloro-5-fluoropyrimidine, 2-chloro-5-iodopyrimidine, 2,4-dichloro-5-fluoropyrimidine, and 2,4-dichloro-5-iodopyrimidine. 5-chloro-2,4,6-trifluoropyrimidine, 2,4,6-trichloropyrimidine, 4,5,6-trichloropyrimidine, 2,4,5-trichloropyrimidine, 2,4,5,6-tetrachloropyrimidine, 2-phenyl-4,6-dichloropyrimidine, 2-methylthio-4,6-dichloropyrimidine, 2-methylsulfonyl-4,6-dichloropyrimidine, 2-amino-4,6-dichloropyrimidine, 5-amino-4,6-dichloropyrimidine, 2,5-diamino-4,6-dichloropyrimidine Zin, 4-amino-2,6-dichloropyrimidine, 4,6-dichloro-5-methoxypyrimidine, 2,4-dichloro-2-methoxypyrimidine, 2,4-dichloro-5-fluoropyrimidine, 5-bromo-2,4-dichloropyrimidine, 2,4-dichloro-5-iodopyrimidine, 4,6-dichloro-2-methylpyrimidine, 4,6-dichloro-5-methylpyrimidine, 2,4-dichloro-6-methylpyrimidine, 2,4-dichloro-5-methylpyrimidine, 2,4-dichloro-5-nitropyrimidine Examples include 4-amino-2-chloro-5-fluoropyrimidine, 5-amino-4,6-dichloro-2-methylpyrimidine, 5-bromo-4-chloro-2-methylthiopyrimidine; 3,6-dichloropyridazine, 3,5-dichloropyridazine, 3,6-dichloro-4-methylpyridazine, 2,3-dichloropyrazine, 2,6-dichloropyrazine, 2,5-dibromopyrazine, 2,6-dibromopyrazine, 2-amino-3,5-dibromopyrazine, and 5,6-dicyano-2,3-dichloropyrazine. These monomers may be used individually or in combination of two or more.

[0105] In the above equations (2-1), (2-2), and (2-3), A1 and A 2 These are, independently, -O-, -S-, or -N(R 2 )- is. A 1 and A 2 When it is -O-, it is preferable in terms of flexibility, solubility, and heat resistance. 1 and A 2 ga-N(R 2 )- is preferable in terms of adhesion, etc. Here, R 2 This is a hydrogen atom and a monovalent hydrocarbon group having 1 to 20 carbon atoms, and may also include an ester group or a sulfonyl group.

[0106] The specific polymer preferably contains a group represented by the following formula (3) as the divalent organic group represented by X in the above formulas (2-1), (2-2), and (2-3).

[0107] [ka]

[0108] In formula (3), Ar1 and Ar2 are independently substituted or unsubstituted aromatic hydrocarbon groups. L is a single bond, -O-, -S-, -N(R 8 ), C=O, -SO2-, P=O, or a divalent organic group. 8 L is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms. y is an integer from 0 to 5. If y is 2 or greater, the multiple Ls may be the same or different. 6 and R 7 Each of these is independently a single bond, a methylene group, or an alkylene group having 2 to 4 carbon atoms.

[0109] The aromatic hydrocarbon groups represented by Ar1 and Ar2 are each preferably aromatic hydrocarbon groups having 6 to 30 carbon atoms, more preferably one of a phenyl group, a naphthyl group, and an anthyl group, and particularly preferably a phenyl group or a naphthyl group.

[0110] Furthermore, the aromatic hydrocarbon groups represented by Ar1 and Ar2 may each have 1 to 8 substituents. From the viewpoint of improving the polymerization reactivity of the monomer, the number of substituents on the aromatic hydrocarbon groups represented by Ar1 and Ar2 is preferably 0 to 8, more preferably 0 to 4, and particularly preferably 0 to 2.

[0111] The substituents are not particularly limited, but include halogen atoms, monovalent hydrocarbon groups having 1 to 20 carbon atoms, monovalent halogenated hydrocarbon groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, alkylthio groups having 1 to 20 carbon atoms, nitro groups, cyano groups, carboxyl groups, sulfonic acid groups, phosphonic acid groups, phosphate groups, hydroxyl groups, primary to tertiary amino groups, salts of carboxyl groups, salts of sulfonic acid groups, salts of phosphonic acid groups, salts of phosphate groups, salts of hydroxyl groups, or salts of primary to tertiary amino groups.

[0112] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms.

[0113] Examples of monovalent hydrocarbon groups having 1 to 20 carbon atoms include the R in formulas (1-1) to (1-3) above. 1 Examples of groups represented by this formula include monovalent hydrocarbon groups having 1 to 20 carbon atoms.

[0114] Examples of monovalent halogenated hydrocarbon groups having 1 to 20 carbon atoms include the R in formulas (1-1) to (1-3) above. 1 Examples of groups represented by this symbol include monovalent hydrocarbon groups having 1 to 20 carbon atoms, in which some or all of the hydrogen atoms are replaced with halogen atoms such as fluorine, chlorine, bromine, or iodine.

[0115] Examples of alkoxy groups having 1 to 20 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, butoxy, pentyloxy, hexyloxy, and octyloxy groups.

[0116] Examples of alkylthio groups having 1 to 20 carbon atoms include methylthio group, ethylthio group, n-propylthio group, isopropylthio group, butylthio group, pentylthio group, hexylthio group, and octylthio group.

[0117] The substituents on the secondary and tertiary amino groups are not particularly limited, but for example, the above R 1 Examples of groups represented by this formula include monovalent hydrocarbon groups having 1 to 20 carbon atoms.

[0118] The cation constituting the cationic moiety in salts of carboxyl groups, sulfonic acid groups, phosphonic acid groups, phosphate groups, hydroxyl groups, and primary to tertiary amino groups is not particularly limited, and Na + These can be known cations such as the following.

[0119] Preferably, the substituents for the aromatic hydrocarbon groups represented by Ar1 and Ar2 are halogen atoms, C1-C3 monovalent hydrocarbon groups, C1-C3 monovalent halogenated hydrocarbon groups, C1-C3 alkoxy groups, C1-C3 alkylthio groups, nitro groups, cyano groups, carboxyl groups, sulfonic acid groups, phosphonic acid groups, phosphoric acid groups, hydroxyl groups, primary--tertiary amino groups, salts of carboxyl groups, salts of sulfonic acid groups, salts of phosphonic acid groups, salts of phosphoric acid groups, salts of hydroxyl groups, or salts of primary--tertiary amino groups, respectively, from the viewpoint of improving the polymerization reactivity of the monomers. More preferably, the substituents are fluorine atoms, chlorine atoms, methyl groups, ethyl groups, fluoromethyl groups, methoxy groups, methylthio groups, nitro groups, cyano groups, carboxyl groups, sulfonic acid groups, phosphonic acid groups, phosphoric acid groups, hydroxyl groups, primary--tertiary amino groups, salts of carboxyl groups, salts of sulfonic acid groups, salts of phosphonic acid groups, salts of phosphoric acid groups, salts of hydroxyl groups, or salts of primary--tertiary amino groups. From a similar viewpoint, a and b are preferably 0 to 8, more preferably 0 to 4, and particularly preferably 0 to 2, respectively. Furthermore, from a similar viewpoint, c and d are preferably 0 to 2, and more preferably 0 or 1, respectively.

[0120] Examples of divalent organic groups with 1 to 20 carbon atoms represented by L include methylene groups, alkylene groups with 2 to 20 carbon atoms, halogenated methylene groups, halogenated alkylene groups with 2 to 20 carbon atoms, and divalent cardi structures.

[0121] Examples of alkylene groups with 2 to 20 carbon atoms represented by L include ethylene, n-propylene, isopropylene, n-butylene, sec-butylene, tert-butylene, neopentylene, 4-methylpentane-2-diyl, and nonane-1,9-diyl.

[0122] Examples of halide methylene groups represented by L include groups in which some or all of the hydrogen atoms of a methylene group are replaced with halogen atoms such as fluorine, chlorine, bromine, or iodine.

[0123] Examples of halogenated alkylene groups having 2 to 20 carbon atoms represented by L include groups in which some or all of the hydrogen atoms of the alkylene group having 2 to 20 carbon atoms exemplified as the group represented by L are replaced with halogen atoms such as fluorine, chlorine, bromine, or iodine.

[0124] Examples of divalent cardi structures represented by L include divalent groups derived from fluorene (i.e., groups with two hydrogen atoms removed from fluorene), divalent groups derived from phenolphthalein (i.e., groups with two hydrogen atoms removed from phenolphthalein), and groups represented by the following formula (L1). In the case of divalent groups derived from fluorene and divalent groups derived from phenolphthalein, some or all of the hydrogen atoms may be substituted with monovalent chain hydrocarbon groups having 1 to 20 carbon atoms, and furthermore, some or all of the hydrogen atoms, including the substituents, may be substituted with fluorine atoms.

[0125] [ka] [In formula (L1), R c It is a divalent alicyclic hydrocarbon group with 5 to 30 ring members.

[0126] R c Examples of divalent alicyclic hydrocarbon groups with 5 to 30 ring members, represented by , include monocyclic alicyclic hydrocarbon groups with 5 to 15 ring members, monocyclic fluorinated alicyclic hydrocarbon groups with 5 to 15 ring members, polycyclic alicyclic hydrocarbon groups with 7 to 30 ring members, and polycyclic fluorinated alicyclic hydrocarbon groups with 7 to 30 ring members.

[0127] Examples of monocyclic alicyclic hydrocarbon groups having 5 to 15 ring members include cyclopentane-1,1-diyl group, cyclohexane-1,1-diyl group, 3,3,5-trimethylcyclohexane-1,1-diyl group, cyclopentene-3,3-diyl group, cyclohexene-3,3-diyl group, cyclooctane-1,1-diyl group, cyclodecane-1,1-diyl group, cyclododecane-1,1-diyl group, and groups in which some or all of the hydrogen atoms of these groups are substituted with monovalent chain hydrocarbon groups having 1 to 20 carbon atoms.

[0128] Examples of the monocyclic fluorinated alicyclic hydrocarbon group having 5 to 15 ring members include groups in which some or all of the hydrogen atoms of the group exemplified as the monocyclic alicyclic hydrocarbon group having 5 to 15 ring members are substituted with fluorine atoms.

[0129] Examples of the polycyclic alicyclic hydrocarbon group having 7 to 30 ring members include norbornane, norbornene, adamantane, and tricyclo[5.2.1.0 2,6 Decane, tricyclo[5.2.1.0 2,6 Examples include groups obtained by removing two hydrogen atoms bonded to one carbon atom of polycyclic alicyclic hydrocarbons such as heptane, pinan, camphan, decalin, nortriclan, perhydroanthracene, perhydroazulene, cyclopentanohydrophenanthrene, and bicyclo[2.2.2]-2-octene, and groups in which some or all of the hydrogen atoms of these groups are substituted with monovalent chain hydrocarbon groups having 1 to 20 carbon atoms.

[0130] Examples of the polycyclic fluorinated alicyclic hydrocarbon group having 7 to 30 ring members include groups in which some or all of the hydrogen atoms of the group exemplified as the polycyclic alicyclic hydrocarbon group having 7 to 30 ring members are substituted with fluorine atoms.

[0131] From the viewpoint of polymer structural stability, L is preferably a single bond, -O-, -S-, -C(O)-, -S(O)-, -S(O)2-, -C(O)-NH-, -C(O)-O-, methylene group, alkylene group having 2 to 5 carbon atoms, haliden methylene group, haliden alkylene group having 2 to 10 carbon atoms, or a divalent cardi structure. Similarly, y is preferably 0 to 4, and more preferably 0 to 3.

[0132] R in equation (3) above 6 and R 7 Examples of alkylene groups with 2 to 4 carbon atoms represented by include ethylene, n-propylene, isopropylene, n-butylene, sec-butylene, and tert-butylene groups. 6 and R 7 From the viewpoint of improving the polymerization reactivity of the monomer, a single bond, a methylene group, or an ethylene group is preferred.

[0133] y is an integer between 0 and 5. From the viewpoint of improving the solubility of the polymer and imparting flexibility, it is preferable that y is 1 or greater. Also, when y is 2 or greater, the multiple L values ​​may be the same or different.

[0134] The content of the repeating units represented by the above formulas (2-1), (2-2), and (2-3) in the specific polymer is preferably 1 to 95 mol%, and more preferably 5 to 80 mol%, when the total amount of all repeating units in the specific polymer is 100 mol%.

[0135] The method for synthesizing the specific polymer is not particularly limited, and known methods can be used. For example, it can be synthesized by heating a monomer that gives at least one repeating unit from among the repeating units represented by formulas (2-1), (2-2), and (2-3) above, and other monomers as needed, together with an alkali metal or the like in an organic solvent.

[0136] The lower limit of the weight-average molecular weight (Mw) of the specific polymer is preferably 500, more preferably 1,000, even more preferably 2,000, and particularly preferably 3,000. The upper limit of the weight-average molecular weight (Mw) is preferably 600,000, more preferably 300,000, and particularly preferably 200,000.

[0137] The lower limit of the glass transition temperature (Tg) of a specific polymer is preferably 70°C, and more preferably 80°C. The upper limit of the glass transition temperature (Tg) is preferably 320°C, and more preferably 300°C, from the viewpoint of processability.

[0138] The nitrogen-containing compound (C) of this embodiment preferably has a group Y represented by the following formula (a) at its terminus. [ka] [In formula (a), Y is a group containing an ethylenically unsaturated double bond having 3 to 50 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 50 carbon atoms, an unsubstituted or substituted aliphatic hydrocarbon group having 6 to 50 carbon atoms, or an unsubstituted nitrogen-containing heteroaromatic ring, and if the aromatic hydrocarbon group or aliphatic hydrocarbon group has substituents, the substituents are groups other than hydroxyl groups.]

[0139] Furthermore, terminal group Y is bonded to the end of the main chain of nitrogen-containing compound (C), forming the terminal portion of nitrogen-containing compound (C). In other words, terminal group Y is R in formulas (1-1) to (1-3) and formulas (2-1) to (2-3) above. 1 and A 1 , and the ends in X (e.g., R in equation (3) above) 6 and R7 is a group different from the group constituting

[0140] The terminal group Y is preferably an aromatic or aliphatic hydrocarbon group with low polarization or a nitrogen-containing heteroaromatic ring in order to improve the dielectric properties. Further, when it contains an ethylenically unsaturated double bond, the crosslinking density can be improved, so heat resistance and curability can be expected.

[0141] Examples of the group having 3 to 50 carbon atoms and containing an ethylenically unsaturated double bond include aromatic ring-containing groups such as 3-isopropenylphenyl group, 4-isopropenylphenyl group, 2-allylphenyl group, 2-methoxy-4-allylphenyl group, 4-(1-propenyl)-2-methoxyphenyl group, 4-vinylbenzyl group, 3-vinylbenzyl group, 2-vinylbenzyl group, etc.; allyl group, acrylic group, methacrylic group, methallyl group.

[0142] Examples of the aromatic hydrocarbon group having 6 to 50 carbon atoms include aryl groups such as phenyl group, biphenyl group, tolyl group, xylyl group, naphthyl group, anthryl group; aralkyl groups such as benzyl group, phenethyl group, phenylpropyl group, naphthylmethyl group.

[0143] Examples of the aliphatic hydrocarbon group having 6 to 50 carbon atoms include monocyclic cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group; polycyclic cycloalkyl groups such as norbornyl group, adamantyl group; monocyclic cycloalkenyl groups such as cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl group; polycyclic cycloalkenyl groups such as norbornenyl group.

[0144] Specific examples of nitrogen-containing heteroaromatic rings in the aforementioned unsubstituted nitrogen-containing heteroaromatic rings include pyrrole rings, pyridine rings, pyrimidine rings, pyrazine rings, pyridazine rings, triazine rings, quinoline rings, isoquinoline rings, quinoxaline rings, phthalazine rings, quinazoline rings, naphthyridine rings, carbazole rings, acridine rings, and phenazine rings. Among the nitrogen-containing heteroaromatic rings, pyrimidine rings are preferred from the viewpoint that polymer (A) can be synthesized with good polymerization reactivity and polymer (A) with excellent solubility in various organic solvents can be easily obtained.

[0145] The substituents in the aforementioned unsubstituted or substituted aromatic hydrocarbon groups having 6 to 50 carbon atoms, unsubstituted or substituted aliphatic hydrocarbon groups having 6 to 50 carbon atoms, and unsubstituted nitrogen-containing heteroaromatic rings are groups other than hydroxyl groups. Specific examples include allyl groups, halogen atoms, monovalent hydrocarbon groups having 1 to 20 carbon atoms, monovalent halogenated hydrocarbon groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, alkylthio groups having 1 to 20 carbon atoms, nitro groups, cyano groups, carboxyl groups, sulfonic acid groups, phosphonic acid groups, phosphoric acid groups, primary to tertiary amino groups, salts of carboxyl groups, salts of sulfonic acid groups, salts of phosphonic acid groups, salts of phosphoric acid groups, and salts of primary to tertiary amino groups. Among these, allyl groups are preferred.

[0146] In the above equations (1-1) to (1-3) or (2-1) to (2-3), R 1 By reacting a monomer that gives the compound with at least one monomer for forming a terminal group Y, selected from the group consisting of monovalent phenols, monovalent amines, monovalent thiols, monovalent aromatics, monovalent aliphatic halides, monovalent acid halides, and monovalent acid anhydrides, a nitrogen-containing compound (C) with terminal groups Y sealed at the ends can be obtained.

[0147] When synthesizing a nitrogen-containing compound (C) in which the terminal group Y contains a double bond, for example, in order to avoid gelation caused by the reaction of double bonds in the monomer for terminal group Y formation during the polymerization of the monomer that serves as the raw material for the main chain, the monomer for terminal group Y formation may be added and reacted after the polymerization of the monomer that serves as the raw material for the main chain.

[0148] Examples of monomers for forming the terminal group Y include monovalent phenol compounds such as t-butylphenol, nonylphenol, 4-isopropenylphenol, 4-vinylphenol, 2-allylphenol, isoeugenol, tocotrienol, α-tocophenol, 4-hydroxyphenylmaleimide, and 2-phenylphenol; monovalent amine compounds such as 4-hexylaniline and diallylamine; monovalent thiol compounds such as 1-octanthiol; monovalent aliphatic halides such as allyl chloride, 4-(chloromethyl)styrene, and 3-(chloromethyl)styrene; monovalent acid halides such as acrylic chloride, methacrylic chloride, crotonoyl chloride, and cinnamoyl chloride; and monovalent acid anhydrides such as acrylic anhydride, crotonic anhydride, and methacrylic anhydride. These monomers may be used individually or in combination of two or more.

[0149] Nitrogen-containing compounds (C) can be synthesized, but commercially available products can also be used, such as "HC-G 0037" manufactured by JSR Corporation.

[0150] The content of nitrogen-containing compound (C) is preferably 5% to 50% by mass, and more preferably 10% to 30% by mass, based on the total amount of polyphenylene ether compound (A), polyfunctional vinyl aromatic copolymer (B), and nitrogen-containing compound (C). By including nitrogen-containing compound (C) in such a content, the resin composition of this embodiment can more reliably obtain excellent adhesion in its cured product.

[0151] <Inorganic filler (D)> The resin composition of this embodiment may optionally contain an inorganic filler (D) to the extent that it does not impair the effects of the present invention. This is thought to improve the low thermal expansion properties of the cured resin composition.Specific examples of inorganic fillers that can be used in this embodiment include, for example, a filler made of at least one selected from the group consisting of silica, alumina, titanium oxide, magnesium oxide and mica, metal hydroxides such as magnesium hydroxide and aluminum hydroxide, talc, aluminum borate, barium sulfate, aluminum nitride, boron nitride, barium titanate, strontium titanate, calcium titanate, aluminum titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and magnesium carbonate such as zirconium tungstate phosphate, anhydrous magnesium carbonate, and calcium carbonate, and boehmite-treated materials thereof.Among these materials, silica, metal hydroxides such as magnesium hydroxide and aluminum hydroxide, aluminum oxide, boron nitride, and barium titanate and strontium titanate are preferred, with silica being more preferred. The silica is not particularly limited and includes, for example, crushed silica, spherical silica, and silica particles.

[0152] These inorganic fillers may be used individually or in combination of two or more types. Furthermore, while the inorganic fillers described above may be used as is, they may also be surface-treated with epoxysilane, vinylsilane, methacrylicsilane, phenylaminosilane, or aminosilane type silane coupling agents. These silane coupling agents can be added using an integral blending method, rather than being pre-surface-treated with the fillers.

[0153] When the resin composition of this embodiment contains an inorganic filler (D), its content is preferably 30 parts by mass or more and 150 parts by mass or less, and more preferably 40 parts by mass or more and 140 parts by mass or less, based on 100 parts by mass of the total of the polyphenylene ether compound (A), the polyfunctional vinyl aromatic copolymer (B), and the nitrogen-containing compound (C).

[0154] <Flame retardant (E)> The resin composition of this embodiment preferably contains a flame retardant (E). By including a flame retardant, the flame retardancy of the cured product of the resin composition can be further enhanced.

[0155] The flame retardant that can be used in this embodiment is not particularly limited. Specifically, in fields where halogen-free is required, a phosphorus-containing flame retardant (phosphorus-based flame retardant) is preferably used. The phosphorus-based flame retardant is not particularly limited, but examples include HCA-based flame retardants, phosphate ester-based flame retardants, phosphazene-based flame retardants, bis-diphenylphosphine oxide-based flame retardants, and phosphinate-based flame retardants. Specific examples of HCA-based flame retardants include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-yl-10-oxide, 10-(2,5-dihydroxyphenyl)-9,10-dihydro9-oxa-10-phosphaphenanthrene-10-oxide, or compounds obtained by pre-reacting these. Specific examples of phosphate ester-based flame retardants include condensed phosphate esters of dixylenyl phosphate. Specific examples of phosphazene-based flame retardants include phenoxyphosphazene. A specific example of a bis-diphenylphosphine oxide-based flame retardant is xylylene bis-diphenylphosphine oxide. A specific example of a phosphinate-based flame retardant is, for example, a phosphinate metal salt of an aluminum dialkylphosphinate.

[0156] Furthermore, in fields where halogen-based flame retardants such as brominated flame retardants are used, for example, ethylenedipentabromobenzene, ethylenebistetrabromoimide, decabromodiphenyl oxide, and tetradecabromodifenoxybenzene, which have a melting point of 300°C or higher, are preferred. It is believed that by using halogen-based flame retardants, the desorption of halogens at high temperatures can be suppressed, thereby preventing a decrease in heat resistance.

[0157] As the flame retardant (E), each of the flame retardants exemplified may be used individually, or two or more may be used in combination.

[0158] <Other thermosetting compounds> The resin composition of this embodiment may further contain thermosetting compounds other than the polyphenylene ether compound (A) and the polyfunctional vinyl aromatic copolymer (B), as long as the effects of the present invention are not impaired.

[0159] Specific examples of thermosetting compounds include acenaphthylene compounds and polyfunctional hydrocarbon compounds having carbon-carbon unsaturated groups other than polyfunctional vinyl aromatic copolymers (B). These can be used individually or in combination of two or more.

[0160] <Other ingredients> The resin composition according to this embodiment may contain components other than those described above (other components) as necessary, as long as they do not impair the effects of the present invention. Examples of other components contained in the resin composition according to this embodiment include catalysts such as reaction initiators and reaction accelerators, polymerization inhibitors, reaction retardants, free radical compounds, flame retardant aids, defoamers, leveling agents, antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, dyes and pigments, dispersants and lubricants and other additives.

[0161] As described above, the resin composition according to this embodiment may contain a reaction initiator (catalyst) and a reaction accelerator. The radical polymerization (curing) reaction can proceed even without a reaction initiator in the resin composition. However, depending on the process conditions, it may be difficult to raise the temperature until curing proceeds, so a reaction initiator may be added. The reaction initiator and reaction accelerator are not particularly limited as long as they can promote the curing reaction of the resin composition. Specifically, examples include azo compounds, peroxides, metal oxides, imidazole compounds, phosphorus-based curing accelerators, amine-based curing accelerators, and the like.

[0162] Specific examples of the azo compounds include, for instance, organic azo compounds such as azobisisobutyronitrile, 2,2'-azobis(2,4,4-trimethylpentane), 2,2'-azobis(N-butyl-2-methylpropionamide), and 2,2'-azobis(2-methylbutyronitrile). Examples of the peroxides include, for instance, organic peroxides such as α,α'-di(t-butylperoxy)diisopropylbenzene (PBP), 2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexine, benzoyl peroxide, 3,3',5,5'-tetramethyl-1,4-diphenoquinone, chloranil, 2,4,6-tri-t-butylphenoxyl, and t-butylperoxyisopropyl monocarbonate.

[0163] When the resin composition of this embodiment contains the reaction initiator, the amount is not particularly limited, but is preferably about 0.1 to 5.0 parts by mass per 100 parts by mass of the total resin components.

[0164] As described above, the resin composition according to this embodiment may optionally contain a free radical compound. By including a free radical compound, the resin composition of this embodiment is thought to be able to further improve moldability while maintaining cured product properties such as Tg. The free radical compound is a compound having a free radical group in its molecule and is a compound different from the polyphenylene ether compound (A), the polyfunctional vinyl aromatic copolymer (B), and the nitrogen-containing compound (C). The free radical compound can slow down the radical reaction by capturing radicals with the free radical group it has in its molecule, thereby slowing down the curing reaction of the resin composition. Examples of the free radical compound include a free radical compound having a 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) structure in its molecule. A commercially available product may be used as the free radical compound, and an example of a commercially available free radical compound is LA-7RD manufactured by ADEKA Corporation.

[0165] If the above-mentioned free radical compound is included, its content is preferably 0.001 to 0.1 parts by mass, and more preferably 0.001 to 0.05 parts by mass, per 100 parts by mass of the total resin components.

[0166] (Prepregs, resin-coated films, metal-clad laminates, wiring boards, and resin-coated metal foils) Next, we will describe prepregs for wiring boards, metal-clad laminates, wiring boards, and resin-coated metal foils using the resin composition of this embodiment.

[0167] Figure 1 is a schematic cross-sectional view showing an example of prepreg 1 according to an embodiment of the present invention.

[0168] As shown in Figure 1, the prepreg 1 according to this embodiment comprises the resin composition or a semi-cured product 2 of the resin composition and a fibrous base material 3. An example of this prepreg 1 is one in which the fibrous base material 3 is present within the resin composition or its semi-cured product 2. That is, this prepreg 1 comprises the resin composition or its semi-cured product and the fibrous base material 3 present within the resin composition or its semi-cured product 2.

[0169] In this embodiment, "semi-cured product" refers to a resin composition that has been partially cured to the extent that it can be further cured. In other words, a semi-cured product is a resin composition that has been partially cured (stage B). For example, when a resin composition is heated, its viscosity gradually decreases at first, then curing begins, and the viscosity gradually increases. In such a case, a semi-cured state would be the state between when the viscosity begins to increase and when it is not yet completely cured.

[0170] The prepreg obtained using the resin composition according to this embodiment may include a semi-cured product of the resin composition as described above, or it may include the uncured resin composition itself. That is, it may be a prepreg comprising a semi-cured product of the resin composition (the resin composition in stage B) and a fibrous substrate, or it may be a prepreg comprising the uncured resin composition (the resin composition in stage A) and a fibrous substrate. Specifically, for example, a resin composition may contain a fibrous substrate. The resin composition or its semi-cured product may be obtained by heat-drying the resin composition.

[0171] The resin composition according to this embodiment is often prepared in a varnish-like form and used as a resin varnish when manufacturing the prepreg, or resin-coated metal foil or metal-clad laminate described later. Such a resin varnish is prepared, for example, as follows.

[0172] First, components that can be dissolved in an organic solvent, such as resin components and reaction initiators, are added to the organic solvent and dissolved. Heating may be performed as needed. Then, inorganic fillers and other components that are not soluble in the organic solvent are added, and the mixture is dispersed using a ball mill, bead mill, planetary mixer, roll mill, etc., until a predetermined dispersion state is reached, thereby preparing a varnish-like resin composition. The organic solvent used here is not particularly limited as long as it dissolves the resin components, such as polyphenylene ether compounds (A), polyfunctional vinyl aromatic copolymers (B), and nitrogen-containing compounds (C), and does not inhibit the curing reaction. Specifically, examples include toluene, methyl ethyl ketone, cyclohexanone, cyclopentanone, methylcyclohexane, dimethylformamide, and propylene glycol monomethyl ether acetate. These may be used individually or in combination of two or more.

[0173] A method for producing the prepreg 1 of this embodiment using the varnish-like resin composition of this embodiment is, for example, to impregnate a fibrous substrate 3 with the resin varnish-like resin composition 2 and then dry it.

[0174] Specific examples of fibrous base materials used in the manufacture of prepregs include glass cloth, aramid cloth, polyester cloth, LCP (liquid crystal polymer) nonwoven fabric, glass nonwoven fabric, aramid nonwoven fabric, polyester nonwoven fabric, pulp paper, and linter paper. When glass cloth is used, a laminate with excellent mechanical strength can be obtained, and flattened glass cloth is particularly preferred. The glass cloth used in this embodiment is not particularly limited, but examples include low dielectric constant glass cloths such as E glass, S glass, NE glass, Q glass, and L glass. Specifically, the flattening process can be carried out, for example, by continuously pressing the glass cloth with a press roll at an appropriate pressure to flatten the yarn. The thickness of the fibrous base material can generally be 0.01 to 0.3 mm.

[0175] The resin varnish (resin composition 2) is impregnated into the fibrous substrate 3 by dipping, coating, etc. This impregnation can be repeated multiple times as needed. Furthermore, it is possible to repeat the impregnation using multiple resin varnishes with different compositions and concentrations to finally adjust to the desired composition (content ratio) and resin amount.

[0176] A fibrous substrate 3 impregnated with resin varnish (resin composition 2) is heated under desired heating conditions, for example, at 80°C or higher and 180°C or lower for 1 minute or more and 10 minutes or less. Heating causes the solvent to evaporate from the varnish, reducing or removing the solvent to obtain a prepreg 1 in a pre-cured state (Stage A) or a semi-cured state (Stage B).

[0177] Furthermore, as shown in Figure 4, the resin-coated metal foil 31 of this embodiment has a structure in which a resin layer 32 containing the above-mentioned resin composition or a semi-cured product of the resin composition and a metal foil 13 are laminated together. That is, the resin-coated metal foil of this embodiment may be a resin-coated metal foil comprising a resin layer containing the resin composition before curing (the resin composition in stage A) and a metal foil, or it may be a resin-coated metal foil comprising a resin layer containing a semi-cured product of the resin composition (the resin composition in stage B) and a metal foil.

[0178] One method for producing such resin-coated metal foil 31 is to apply a resin varnish-like resin composition, as described above, to the surface of a metal foil 13 such as copper foil, and then dry it. Examples of such application methods include bar coaters, comma coaters, die coaters, roll coaters, gravure coaters, and the like.

[0179] The metal foil 13 can be any metal foil used in metal-clad laminates, wiring boards, etc., for example, copper foil and aluminum foil.

[0180] Furthermore, as shown in Figure 5, the resin-coated film 41 of this embodiment has a structure in which a resin layer 42 containing the above-mentioned resin composition or a semi-cured product of the resin composition and a film support substrate 43 are laminated together. That is, the resin-coated film of this embodiment may be a resin-coated film comprising the resin composition before curing (the resin composition in stage A) and a film support substrate, or it may be a resin-coated film comprising a semi-cured product of the resin composition (the resin composition in stage B) and a film support substrate.

[0181] As a method for producing such a resin-coated film 41, for example, a resin varnish-like resin composition as described above can be applied to the surface of a film support substrate 43, and then the solvent can be evaporated from the varnish to reduce the amount of solvent, or the solvent can be removed, thereby obtaining a resin-coated film in a pre-cured state (Stage A) or a semi-cured state (Stage B).

[0182] Examples of the film support substrate include electrically insulating films such as polyimide film, PET (polyethylene terephthalate) film, polyethylene naphthalate film, polyester film, polyparabanic acid film, polyether ether ketone film, polyphenylene sulfide film, aramid film, polycarbonate film, and polyarylate film.

[0183] In addition, in the resin-coated film and resin-coated metal foil of this embodiment, similar to the prepreg described above, the resin composition or its semi-cured product may be obtained by drying or heat-drying the resin composition.

[0184] The thickness of the metal foil 13 and the film support substrate 43 can be set appropriately according to the desired purpose. For example, the metal foil 13 can be approximately 0.2 to 70 μm thick. If the thickness of the metal foil is, for example, 10 μm or less, a carrier-equipped copper foil with a release layer and carrier may be used to improve handling. The resin varnish is applied to the metal foil 13 and the film support substrate 43 by coating, and this can be repeated multiple times as needed. In this case, it is also possible to repeatedly coat using multiple resin varnishes with different compositions and concentrations to finally adjust to the desired composition (content ratio) and amount of resin.

[0185] The drying or heat drying conditions in the manufacturing method of the resin-coated metal foil 31 and resin-coated film 41 are not particularly limited, but after applying a resin varnish-like resin composition to the metal foil 13 or film support substrate 43, the resin is heated under desired heating conditions, for example, at 50 to 180°C for about 0.1 to 10 minutes, to volatilize the solvent from the varnish and reduce or remove the solvent, thereby obtaining the resin-coated metal foil 31 or resin-coated film 41 in a pre-cured state (A stage) or a semi-cured state (B stage).

[0186] The resin-coated metal foil 31 and the resin-coated film 41 may be provided with a cover film or the like, if necessary. Providing a cover film can prevent the incorporation of foreign matter. The cover film is not particularly limited as long as it can be peeled off without damaging the form of the resin composition, but for example, polyolefin film, polyester film, TPX film, films formed by providing a release agent layer on these films, and paper obtained by laminating these films onto a paper substrate can be used.

[0187] As shown in Figure 2, the metal-clad laminate 11 of this embodiment is characterized by having an insulating layer 12 containing a cured product of the resin composition or a cured product of the prepreg described above, and a metal foil 13. The metal foil 13 used in the metal-clad laminate 11 can be the same as the metal foil 13 described above.

[0188] Furthermore, the metal-clad laminate 11 of this embodiment can also be made using the resin-coated metal foil 31 or resin-coated film 41 described above.

[0189] As a method for producing a metal-clad laminate using the prepreg 1, resin-coated metal foil 31, or resin-coated film 41 obtained as described above, one or more sheets of the prepreg 1, resin-coated metal foil 31, or resin-coated film 41 are stacked, and then metal foil 13 such as copper foil is stacked on both sides or one side of the stack. This is then heated and pressurized to create a laminate that is metal-clad on both sides or on one side. The heating and pressurizing conditions can be appropriately set depending on the thickness of the laminate to be manufactured and the type of resin composition, but for example, the temperature can be set to 170-230°C, the pressure to 1.5-5.0 MPa, and the time to 60-150 minutes.

[0190] Alternatively, the metal-clad laminate 11 may be manufactured by forming a film-like resin composition on a metal foil 13 and then heating and pressurizing it, without using a prepreg 1 or the like.

[0191] As shown in Figure 3, the wiring board 21 of this embodiment has an insulating layer 12 containing a cured product of the resin composition or a cured product of the prepreg described above, and wiring 14.

[0192] The resin composition of this embodiment is suitably used as a material for the insulating layer of a wiring board. As a method for manufacturing the wiring board 21, for example, a wiring board 21 can be obtained by etching the metal foil 13 on the surface of the metal-clad laminate 11 obtained above to form circuits (wirings), thereby providing a conductor pattern (wirings 14) as a circuit on the surface of the laminate. In addition to the method described above, other methods for forming circuits include, for example, circuit formation by the semi-additive process (SAP) or the modified semi-additive process (MSAP).

[0193] The prepregs, resin-coated films, and resin-coated metal foils obtained using the resin composition of this embodiment are extremely useful for industrial applications because, in their cured form, they possess excellent low dielectric properties, high Tg, and adhesion (especially copper foil peel strength). Furthermore, the metal-clad laminates and wiring boards obtained by curing them also possess the same excellent properties.

[0194] This specification discloses various aspects of technology as described above, but the main technologies are summarized below.

[0195] A resin composition according to a first aspect of the present invention is characterized by comprising a polyphenylene ether compound (A) having a carbon-carbon unsaturated double bond in its molecule, a polyfunctional vinyl aromatic copolymer (B) containing repeating units (b1) derived from a divinyl aromatic copolymer and repeating units (b2) derived from a monovinyl aromatic compound, and a nitrogen-containing compound (C) having at least one of the structural units represented by the above formulas (1-1), (1-2), and (1-3).

[0196] A resin composition according to a second aspect of the present invention is characterized in that, in the resin composition according to the first aspect, the nitrogen-containing compound (C) has at least one of the structural units represented by the above formulas (2-1), (2-2), and (2-3).

[0197] A resin composition according to a third aspect of the present invention is characterized in that, in the resin composition of the first or second aspect, the divalent organic group represented by X in formulas (2-1) to (2-3) contains the group represented by formula (3).

[0198] A third aspect of the present invention is a resin composition according to any of the first to third aspects, characterized in that the nitrogen-containing compound (C) has a group Y represented by the above formula (a) at its terminus.

[0199] A resin composition according to a fourth aspect of the present invention is characterized in that, in any of the first to fourth aspects of the resin composition, the content of nitrogen-containing compound (C) is 5% by mass or more and 50% by mass or less, based on the total amount of polyphenylene ether compound (A), polyfunctional vinyl aromatic copolymer (B), and nitrogen-containing compound (C).

[0200] A fifth aspect of the present invention is a resin composition according to any of the first to fifth aspects, characterized in that the polyphenylene ether compound (A) is a polyphenylene ether compound having at least one of the groups represented by formula (4) or formula (5).

[0201] The seventh aspect of the present invention is characterized in that, in any of the first to sixth aspects of the resin composition, the content of the polyfunctional vinyl aromatic copolymer (B) is 40% by mass or more and 80% by mass or less, based on the total amount of the polyphenylene ether compound (A), the polyfunctional vinyl aromatic copolymer (B), and the nitrogen-containing compound (C).

[0202] The eighth aspect of the present invention is characterized in that, in the resin composition of any of the first to seventh aspects, it further contains an inorganic filler (D), and the amount of inorganic filler (D) is 30 parts by mass or more and 150 parts by mass or less, based on 100 parts by mass of the total of the polyphenylene ether compound (A), the polyfunctional vinyl aromatic copolymer (B), and the nitrogen-containing compound (C).

[0203] A resin composition according to the ninth aspect of the present invention is characterized in that it further contains a flame retardant (E) in the resin composition of any of the first to eighth aspects.

[0204] A prepreg according to the tenth aspect of the present invention comprises a resin composition according to any of the first to ninth aspects or a semi-cured product of the resin composition, and a fibrous substrate.

[0205] A resin-coated film according to the 11th aspect of the present invention comprises a resin layer containing a resin composition according to any of the 1st to 9th aspects or a semi-cured product of the resin composition, and a support film.

[0206] A resin-coated metal foil according to the twelfth aspect of the present invention comprises a resin layer containing a resin composition according to any of the first to ninth aspects or a semi-cured product of the resin composition, and a metal foil.

[0207] A metal-clad laminate according to the thirteenth aspect of the present invention comprises an insulating layer containing a cured product of a resin composition according to any of the first to ninth aspects or a cured product of a prepreg according to the tenth aspect, and a metal foil.

[0208] A wiring board according to the 14th aspect of the present invention comprises an insulating layer containing a cured product of a resin composition according to any of the 1st to 9th aspects or a cured product of a prepreg according to the 10th aspect, and wiring.

[0209] The present invention will be described in more detail below with reference to examples, but the scope of the present invention is not limited thereto. [Examples]

[0210] First, the components used in preparing the resin composition in this embodiment will be described.

[0211] <Polyphenylene ether compound (A)> • Synthesis of modified PPE1: Modified polyphenylene ether compound 2 was obtained by reacting polyphenylene ether with chloromethylstyrene. Specifically, first, 200 g of polyphenylene ether (SA90, manufactured by SABIC Innovative Plastics, with an intrinsic viscosity (IV) of 0.083 dl / g, 1.9 terminal hydroxyl groups, and a weight molecular weight of Mw1700), 30 g of a mixture of p-chloromethylstyrene and m-chloromethylstyrene in a mass ratio of 50:50 (chloromethylstyrene: CMS, manufactured by Tokyo Chemical Industry Co., Ltd.), 1.227 g of tetra-n-butylammonium bromide as a phase transfer catalyst, and 400 g of toluene were charged into a 1 liter three-necked flask equipped with a temperature controller, a stirrer, a cooling device, and a dropping funnel, and the mixture was stirred. The mixture was then stirred until the polyphenylene ether, chloromethylstyrene, and tetra-n-butylammonium bromide dissolved in the toluene. During this process, the mixture was gradually heated until the liquid temperature reached 75°C. Then, an aqueous solution of sodium hydroxide (20 g sodium hydroxide / 20 g water) was added dropwise to the solution over 20 minutes as an alkali metal hydroxide. After that, the mixture was stirred at 75°C for 4 hours. Next, the contents of the flask were neutralized with 10% by mass hydrochloric acid, and then a large amount of methanol was added. This caused a precipitate to form in the liquid in the flask, that is, the products contained in the reaction mixture in the flask were reprecipitated. This precipitate was then removed by filtration, washed three times with a methanol-water mixture in a mass ratio of 80:20, and then dried under reduced pressure at 80°C for 3 hours.

[0212] The obtained solid, 1 The sample was analyzed by 1H-NMR (400 MHz, CDCl3, TMS). NMR analysis revealed peaks originating from ethenylbenzyl at 5–7 ppm. This confirmed that the obtained solid was a vinylbenzylated polyphenylene ether (a polyphenylene ether compound with vinylbenzyl groups at its termini).

[0213] Furthermore, the molecular weight distribution of the modified polyphenylene ether was measured using GPC. The weight-average molecular weight (Mw) was calculated from the obtained molecular weight distribution, and the result was 2300.

[0214] Furthermore, the number of terminal functionalities in modified polyphenylene ethers was measured as follows: First, the modified polyphenylene ether was accurately weighed. Let the weight be X (mg). Then, this weighed modified polyphenylene ether was dissolved in 25 mL of methylene chloride, and 100 μL of an ethanol solution of 10% by mass of tetraethylammonium hydroxide (TEAH) (TEAH:ethanol (volume ratio) = 15:85) was added to the solution. The absorbance (Abs) at 318 nm was then measured using a UV spectrophotometer (UV-1600, Shimadzu Corporation). From the measurement results, the number of terminal hydroxyl groups of the modified polyphenylene ether was calculated using the following formula. Residual OH amount (μmol / g) = [(25×Abs) / (ε×OPL×X)]×106 Here, ε represents the extinction coefficient, which is 4700 L / mol·cm. OPL is the cell path length, which is 1 cm.

[0215] Furthermore, the calculated residual OH amount (number of terminal hydroxyl groups) of the modified polyphenylene ether was almost zero, indicating that the hydroxyl groups of the polyphenylene ether before modification were almost completely modified. From this, it was found that the decrease from the number of terminal hydroxyl groups of the polyphenylene ether before modification corresponds to the number of terminal hydroxyl groups of the polyphenylene ether before modification. In other words, the number of terminal hydroxyl groups of the polyphenylene ether before modification corresponds to the number of terminal functional groups of the modified polyphenylene ether. That is, the number of terminal functional groups was 1.8. This will be referred to as "Polyphenylene Ether Compound 2". Here, the number of terminal hydroxyl groups refers to the average number of phenolic hydroxyl groups at the molecular ends per polyphenylene ether molecule.

[0216] · Modified PPE2: A polyphenylene ether compound having a methacryloyl group at the end (「SA9000」 manufactured by SABIC Innovative Plastics, a modified polyphenylene ether obtained by modifying the terminal hydroxyl group of polyphenylene ether with a methacryloyl group, weight average molecular weight Mw 2000)

[0217] <Polyfunctional vinyl aromatic polymer (B)> A polyfunctional vinyl aromatic polymer was obtained based on the following method: 3.0 mol (390.6 g) of divinylbenzene, 1.8 mol (229.4 g) of ethylvinylbenzene, 10.2 mol (1066.3 g) of styrene, and 15.0 mol (1532.0 g) of n-propyl acetate were charged into a 5.0 L reactor, and 600 mmol of boron trifluoride diethyl ether complex was added at 70°C and reacted for 4 hours. After the polymerization solution was terminated with an aqueous sodium hydrogen carbonate solution, the oil layer was washed 3 times with pure water, and volatile components were removed under reduced pressure at 60°C to recover the copolymer. The obtained copolymer was weighed, and it was confirmed that 896.7 g of copolymer B was obtained. The Mn of the obtained copolymer B was 2980, Mw was 41300, and Mw / Mn was 13.9. 13 C-NMR and 1 By performing H-NMR analysis, resonance lines derived from each monomer unit were observed in copolymer A. Based on the NMR measurement results and GC analysis results, the constitutional units of copolymer A were calculated as follows. The constitutional units of copolymer B were calculated as follows. Structural unit (b1) derived from divinylbenzene: 30.4 mol% (33.1 wt%) Structural unit (b2-2) derived from ethylvinylbenzene: 12.2 mol% (14.2 wt%) Structural unit (b2-1) derived from styrene: 57.4 mol% (52.7 wt%) Structural unit (b1-1) having a residual vinyl group derived from divinylbenzene: 23.9 mol% (25.9 wt%)

[0218] <Nitrogen-containing compound (C)> · Nitrogen-containing compound: 「HC-G 0037」 (manufactured by JSR Corporation)

[0219] <Flame retardant (E)> · Flame retardant 1: Brominated flame retardant, "SAYTEX8010" (manufactured by Albemarle Japan Co., Ltd.) · Flame retardant 2: Phosphorus-based flame retardant, "PQ60" (manufactured by Jin-yi Chemical Co., Ltd.)

[0220] <Free radical compound> · Free radical compound: Adeka Stab "LA-7RD" (manufactured by ADEKA Corporation)

[0221] <Reaction initiator> · Azo compound: 2,2'-azobis(2,4,4-trimethylpentane) "VR-110" (manufactured by Fujifilm Wako Pure Chemical Corporation)

[0222] <Inorganic filler (D)> · Silica filler: Spherical silica "EQ2410-SMC" (manufactured by Zhejiang Sanshiji New Material Technology Co., Ltd.)

[0223] <Examples 1 to 6 and Comparative Examples 1 to 3> [Preparation method] (Resin varnish) First, each component was added to a toluene solvent at the blending ratio (parts by mass) shown in Table 1 so that the resin component had a solid content concentration of 65% by mass and mixed. The obtained mixture was stirred for 120 minutes. Then, an inorganic filler (silica filler) was added to the obtained mixture, and after being dispersed in advance with a stirrer, the filler was dispersed with a bead mill. By doing so, a varnish-like resin composition (varnish) was obtained.

[0224] (Preparation of evaluation substrate) A prepreg and an evaluation substrate (metal-clad laminate) were obtained as follows.

[0225] First, the obtained varnish was impregnated into a fibrous substrate (glass cloth: Asahi Kasei Corporation's #1078 type, L2 glass), and then heated and dried at 120°C for 3 minutes to produce a prepreg with a thickness of 100 μm. At that time, the content of the components constituting the resin composition relative to the prepreg (resin content) was adjusted to approximately 74% by mass.

[0226] Next, an evaluation substrate (metal-clad laminate) was obtained as follows.

[0227] Four of the obtained prepregs were stacked together, and copper foil (Fukuda Metal Foil & Powder Industry Co., Ltd. "CF-T4X-SV-18", copper foil thickness: 18 μm) was placed on both sides. This was used as the pressure-bearing body, and it was heated to a temperature of 200°C at a heating rate of 3°C / min. By heating and pressurizing it at 200°C for 120 minutes under a pressure of 3 MPa, an evaluation substrate (metal-clad laminate) with a resin layer thickness of approximately 400 μm was obtained, with copper foil bonded to both sides.

[0228] Using the evaluation substrate (metal-clad laminate) prepared as described above, an evaluation test was performed using the method shown below.

[0229] <Evaluation Test 1> The following tests were performed on the evaluation substrates of the examples and comparative examples. (Dielectric properties: Dielectric loss tangent (Df)) An unclad plate, obtained by etching away the copper foil from the aforementioned 400 μm thick evaluation substrate (metal-clad laminate), was used as a test specimen, and its dielectric loss tangent (Df) at 10 GHz was measured using the cavity resonator perturbation method. Specifically, a network analyzer (N5230A manufactured by Keysight Technologies, Inc.) was used to measure the dielectric loss tangent of the evaluation substrate at 10 GHz. In this test, a Df of 0.00150 or less was considered a pass.

[0230] (Glass transition temperature (Tg)) The outer layer copper foil of the evaluation substrate (metal-clad laminate) was etched entirely, and for the obtained sample, the Tg was measured using the viscoelastic spectrometer "DMA7100" manufactured by Hitachi High-Tech Corporation. At this time, dynamic viscoelastic measurement (DMA) was performed with a tensile modulus at a frequency of 1 Hz, and the temperature at which tanδ showed a maximum when the temperature was raised from room temperature to 300 °C at a rate of temperature increase of 5 °C / min was defined as Tg. In this test, if the Tg is 150 °C or higher, it is considered qualified.

[0231] The above results are shown in Table 1.

[0232]

Table 1

[0233] (Discussion) As is clear from the results shown in Table 1, it was confirmed that the cured product having low dielectric characteristics (Df) and high Tg could be obtained with the resin composition of the present invention. On the other hand, in the resin compositions of Comparative Examples 1 and 4 that do not contain the polyphenylene ether compound (A), a sufficiently high Tg could not be obtained. Further, in Comparative Example 2 using a resin composition that does not contain the nitrogen-containing compound (C), the dielectric characteristics were insufficient. And in Comparative Example 3 using a resin composition that does not contain the polyfunctional vinyl aromatic copolymer (B), the results showed that both the dielectric characteristics and Tg were insufficient.

[0234] <Evaluation Test 2> Regarding the evaluation substrate of the example, the following test was further conducted.

[0235] (Dielectric characteristics: relative permittivity (Dk)) An unclad board obtained by removing the copper foil from the evaluation substrate (metal-clad laminate) with a thickness of 400 μm by etching was used as a test piece, and the relative permittivity (Dk) at 10 GHz was measured by the cavity resonator perturbation method. Specifically, using a network analyzer (N5230A manufactured by Keysight Technologies, Inc.), the dielectric tangent of the evaluation substrate at 10 GHz was measured. In this test, if Dk is 3.3 or less, it is considered good.

[0236] (Copper foil peel strength) The copper foil was peeled off the evaluation substrate (metal-clad laminate), and the peel strength was measured in accordance with JIS C 6481 (1996). Specifically, the evaluation substrate was made 10 mm wide x 100 mm long, and the copper foil was peeled off at a speed of 50 mm / min using a tensile testing machine, and the peel strength (N / mm) at that time was measured. This peel strength is the copper foil peel strength, and it was found that the higher this value, the better the adhesion of the metal foil (copper foil). In this test, a measured copper foil peel strength of 0.40 N / mm or higher was judged to be good.

[0237] The results are shown in Table 2.

[0238] [Table 2]

[0239] (Consideration) As is clear from the results shown in Table 2, it was confirmed that the resin composition of the present invention can produce a cured product with low Dk and good adhesion (peel strength). [Explanation of symbols]

[0240] 1 Prepreg 2. Resin composition or semi-cured resin composition 3. Fibrous base material 11 Metal-clad laminate 12 Insulating layer 13 Metal foil 14 Wiring 21 Wiring board 31 Resin-coated metal foil 32, 42 Resin layer 41 Resin-coated film 43 Support film

Claims

1. A polyphenylene ether compound (A) having a carbon-carbon unsaturated double bond in its molecule, A polyfunctional vinyl aromatic copolymer (B) containing repeating units (b1) derived from a divinyl aromatic copolymer and repeating units (b2) derived from a monovinyl aromatic compound, A resin composition comprising a nitrogen-containing compound (C) having at least one structural unit represented by the following formulas (1-1), (1-2), and (1-3). 【Chemistry 1】 [In formulas (1-1) to (1-3), R １ Each of these is independently a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a nitro group, a cyano group, a primary to tertiary amino group, or a salt of a primary to tertiary amino group. Each of these is independently an integer from 0 to 2. When n is 2, multiple R １ These elements may be identical or different, and may be joined in any combination to form part of a ring structure.

2. The resin composition according to claim 1, wherein the nitrogen-containing compound (C) has at least one of the structural units represented by the following formulas (2-1), (2-2), and (2-3). 【Chemistry 2】 [In formulas (2-1) to (2-3), R １ And n is R in the above equations (1-1) to (1-3). １ And is the same as n. A １ and A ２ These are independently -O-, -S-, or -N(R) ２ ) - is R ２ X is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms. X is a divalent organic group.

3. The resin composition according to claim 2, wherein the divalent organic group represented by X in formulas (2-1) to (2-3) contains a group represented by the following formula (3). 【Transformation 3】 〔In formula (3), Ar １ and Ar ２ are each independently a substituted or unsubstituted aromatic hydrocarbon group. L is a single bond, -O-, -S-, -N(R ８ ), C=O, -SO2-, P=O, or a divalent organic group. R ８ is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms. y is an integer from 0 to 5. When y is 2 or more, the plurality of Ls may be the same or different from each other. R ６ and R ７ are each independently a single bond, a methylene group, or an alkylene group having 2 to 4 carbon atoms.〕

4. The resin composition according to claim 1, wherein the nitrogen-containing compound (C) has a group Y represented by the following formula (a) at its terminus. 【Chemistry 4】 [In formula (a), Y is a group containing an ethylenically unsaturated double bond having 3 to 50 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon group having 6 to 50 carbon atoms, an unsubstituted or substituted aliphatic hydrocarbon group having 6 to 50 carbon atoms, or an unsubstituted nitrogen-containing heteroaromatic ring, and if the aromatic hydrocarbon group or aliphatic hydrocarbon group has substituents, the substituents are groups other than hydroxyl groups.]

5. The content of nitrogen-containing compound (C) is polyphenylene ether compound (A), polyfunctional vinyl A total amount of 5% by mass or more of the total amount of aromatic copolymer (B) and nitrogen-containing compound (C) The resin composition according to claim 1, wherein the amount is 0% by mass or less.

6. The resin composition according to claim 1, wherein the polyphenylene ether compound (A) is a polyphenylene ether compound having at least one of the groups represented by the following formula (4) or formula (5). 【Transformation 5】 [In formula (4), s represents an integer from 0 to 10. Z represents an arylene group. R ９ ~R １１ Each of these independently represents either a hydrogen atom or an alkyl group. 【Transformation 6】 [In formula (5), R １２ This represents a hydrogen atom or an alkyl group.

7. The resin composition according to claim 1, wherein the content of the polyfunctional vinyl aromatic copolymer (B) is 40% by mass or more and 80% by mass or less, based on the total amount of the polyphenylene ether compound (A), the polyfunctional vinyl aromatic copolymer (B), and the nitrogen-containing compound (C).

8. Further containing an inorganic filler (D), The resin composition according to claim 1, wherein the content of the inorganic filler (D) is 30 parts by mass or more and 150 parts by mass or less, based on 100 parts by mass of the total of the polyphenylene ether compound (A), the polyfunctional vinyl aromatic copolymer (B), and the nitrogen-containing compound (C).

9. The resin composition according to claim 1, further comprising a flame retardant (E).

10. A prepreg comprising a resin composition according to any one of claims 1 to 9 or a semi-cured product of the resin composition, and a fibrous substrate.

11. A resin-coated film comprising a resin layer containing the resin composition described in any one of claims 1 to 9 or a semi-cured product of the resin composition, and a support film.

12. A resin-coated metal foil comprising a resin layer containing the resin composition described in any one of claims 1 to 9 or a semi-cured product of the resin composition, and a metal foil.

13. A metal-clad laminate comprising an insulating layer containing a cured product of the resin composition according to any one of claims 1 to 9, and a metal foil.

14. A wiring substrate comprising an insulating layer containing a cured product of a resin composition according to any one of claims 1 to 9, and wiring.

15. A metal-clad laminate comprising an insulating layer containing a cured prepreg according to claim 10, and a metal foil.

16. A wiring board comprising an insulating layer containing a cured prepreg according to claim 10, and wiring.

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