Resin composition, prepreg, film with resin, metal foil with resin, metal foil-clad laminate, and wiring board

Abstract

One aspect of the present invention relates to a resin composition comprising: a modified polyphenylene ether compound whose terminal is modified by a substituent having a carbon-carbon unsaturated double bond; and a free radical compound, wherein the free radical compound has at least one free radical selected from the group consisting of structures represented by formula (1), formula (2), formula (3) and formula (4) in the molecule.

Description

Technical Field

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

[0002] For various electronic devices, as the amount of information processing increases, the installation technology of high integration of semiconductor devices, high density of wiring, and multilayering is developing day by day. In addition, as wiring boards used in various electronic devices, wiring boards that can cope with high frequencies, such as millimeter-wave radar substrates in vehicle-mounted applications, are sought. For wiring boards used in various electronic devices, in order to increase the transmission speed of signals, it is required to reduce the loss during signal transmission; for wiring boards that can cope with high frequencies, it is particularly necessary to meet the above requirements. In order to meet this requirement, the substrate material used to constitute the substrate of the wiring boards used in various electronic devices is required to have a low dielectric constant and dielectric loss factor.

[0003] As such a base material, for example, a curable composition has been proposed, which comprises a radical polymerizable compound having an unsaturated bond in the molecule, a specified amount of an inorganic filler containing a metal oxide, and a specified amount of a dispersant having an acidic group and a basic group (Patent Document 1).

[0004] Patent document 1 discloses a curable composition that can produce a cured product having excellent dielectric properties and heat resistance and a low thermal expansion coefficient. It is believed that a wiring board obtained by using a resin composition having low dielectric properties such as a dielectric constant and a dielectric loss factor as described in Patent document 1 can reduce the loss during signal transmission.

[0005] On the other hand, the dielectric properties of the wiring board are required not to deteriorate even after long-term use. In order to prevent the dielectric properties of the wiring board from deteriorating over a long period of time, the electrical properties (dielectric loss tangent in the embodiment) of the cured product constituting the wiring board need to be kept constant.

[0006] Generally, as a method for observing the change of electrical characteristics over a long period of time, there is a treatment test in a thermal environment. Even in a thermal environment, the change of the electrical characteristics of the cured product is required to be small.

[0007] Furthermore, the base material of the wiring board is required to maintain its low dielectric property even when it absorbs water so that the wiring board can be used even in a high humidity environment.

[0008] That is, the base material constituting the wiring board base material is required to have dielectric properties that are not affected by high temperature and water absorption, so that the wiring board can be used even in a high temperature environment and a high humidity environment.

[0009] Furthermore, in order to be applied to wiring boards, especially multi-layer laminated wiring boards, it is necessary to fill the base material (insulating layer forming material) into the circuit pattern (between wirings), and for this purpose, sufficient resin fluidity is required. In this regard, the above-mentioned prior art does not record a technology for filling the forming material into the fine circuit pattern (between wirings).

[0010] Prior art literature

[0011] Patent Literature

[0012] Patent Document 1: Japanese Patent Publication No. 2016-56367 Summary of the invention

[0013] The present invention is made in view of the above circumstances, and its object is to provide a resin composition that can obtain a cured product with low dielectric properties, high heat resistance, and is not easily affected by changes in the external environment, and has formability that can be applied to a laminated wiring board. In addition, the present invention aims to provide a prepreg, a film with a resin, a metal foil with a resin, a metal foil-clad laminate, and a wiring board obtained by using the resin composition.

[0014] The present inventors have conducted various studies and found that the above-mentioned object can be achieved by the following configuration. The inventors have further conducted studies and have completed the present invention.

[0015] One aspect of the present invention relates to a resin composition comprising: a modified polyphenylene ether compound whose terminal is modified with a substituent having a carbon-carbon unsaturated double bond; and a free radical compound, wherein the free radical compound has at least one free radical selected from the group consisting of structures represented by the following formula (1), formula (2), formula (3) and formula (4) in the molecule. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 This is a schematic cross-sectional view showing an example of a prepreg according to an embodiment of the present invention.

[0017] Figure 2 This is a schematic cross-sectional view showing an example of a metal foil-clad laminate according to an embodiment of the present invention.

[0018] Figure 3 This is a schematic cross-sectional view showing an example of a wiring board according to an embodiment of the present invention.

[0019] Figure 4 This is a schematic cross-sectional view showing an example of a metal foil with resin according to an embodiment of the present invention.

[0020] Figure 5 This is a schematic cross-sectional view showing an example of a film with resin according to an embodiment of the present invention. DETAILED DESCRIPTION

[0021] Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to these descriptions.

[0022] [Resin composition]

[0023] An embodiment of the present invention relates to a resin composition comprising: a modified polyphenylene ether compound whose terminal is modified with a substituent having a carbon-carbon unsaturated double bond; and a free radical compound, wherein the free radical compound has at least one free radical selected from the group consisting of structures represented by the following formula (1), formula (2), formula (3) and formula (4) in the molecule.

[0024]

[0025] By making the resin composition containing the modified polyphenylene ether compound contain a radical compound having the above structure, a resin composition having low dielectric properties and high heat resistance can be obtained, and a cured product can be obtained which can well maintain low dielectric properties even after heat treatment and water absorption treatment, and has excellent moldability.

[0026] That is, according to the present invention, a resin composition having excellent formability that can be filled into a circuit pattern and can obtain a cured product having low dielectric properties and high heat resistance and can well maintain low dielectric properties even after heat treatment or water absorption treatment can be provided. In addition, according to the present invention, by using the resin composition, a prepreg, a film with resin, a metal foil with resin, a metal foil-clad laminate, and a wiring board having excellent performance can be provided.

[0027] This is considered to be because the addition of the radical compound can improve the moldability while maintaining the cured product characteristics such as high Tg to a certain extent.

[0028] First, each component of the resin composition according to the present embodiment will be described.

[0029] (Modified polyphenylene ether compound)

[0030] The modified polyphenylene ether compound of this embodiment is not particularly limited as long as the terminal is modified with a substituent having a carbon-carbon unsaturated double bond. It is believed that the inclusion of the modified polyphenylene ether compound can provide a resin composition that can obtain a cured product having low dielectric properties and high heat resistance.

[0031] The substituent having a carbon-carbon unsaturated double bond is not particularly limited, and examples of the substituent include a substituent represented by the following formula (5) and a substituent represented by the following formula (6).

[0032]

[0033] In formula (5), p represents an integer of 0 to 10. In addition, Z represents an arylene group. In addition, R1 to R3 are each independent. That is, R1 to R3 may be the same group or different groups. In addition, R1 to R3 represent a hydrogen atom or an alkyl group.

[0034] In addition, in formula (5), when p is 0, it means that Z is directly bonded to the terminal of the polyphenylene ether.

[0035] The arylene group of Z is not particularly limited. Examples of the arylene group include monocyclic aromatic groups such as phenylene; polycyclic aromatic groups such as naphthalene rings that are not monocyclic aromatic groups; and the like. In addition, the arylene group also includes derivatives in which the hydrogen atoms bonded to the aromatic ring are substituted by functional groups such as alkenyl, alkynyl, formyl, alkylcarbonyl, alkenylcarbonyl or alkynylcarbonyl. In addition, the alkyl group is not particularly limited, and for example, is preferably an alkyl group having 1 to 18 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms. Specifically, examples include methyl, ethyl, propyl, hexyl and decyl.

[0036]

[0037] In formula (6), R4 represents a hydrogen atom or an alkyl group. The alkyl group is not particularly limited, and is preferably an alkyl group having 1 to 18 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms. Specific examples thereof include methyl, ethyl, propyl, hexyl, and decyl groups.

[0038] Preferred specific examples of the substituent represented by the formula (5) include substituents containing a vinylbenzyl group, etc. Examples of the substituent containing a vinylbenzyl group include substituents represented by the following formula (10), etc.

[0039] Examples of the substituent represented by the formula (6) include an acrylate group and a methacrylate group.

[0040]

[0041] More specifically, examples of the substituent include vinylbenzyl groups (vinylbenzyl groups) such as p-vinylbenzyl and m-vinylbenzyl, vinylphenyl groups, acrylate groups, and methacrylate groups.

[0042] The modified polyphenylene ether compound has a polyphenylene ether chain in the molecule, and preferably has a repeating unit represented by the following formula (11) in the molecule.

[0043]

[0044] In formula (11), t represents 1 to 50. In addition, R5 to R8 are each independent. That is, R5 to R8 may be the same group or different groups. In addition, R5 to R8 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 them, a hydrogen atom and an alkyl group are preferred.

[0045] In R5 to R8, as each functional group listed above, specifically, the following groups can be mentioned.

[0046] The alkyl group is not particularly limited, and is preferably an alkyl group having 1 to 18 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a hexyl group, and a decyl group.

[0047] The alkenyl group is not particularly limited, but is preferably an alkenyl group having 2 to 18 carbon atoms, and more preferably an alkenyl group having 2 to 10 carbon atoms. Specific examples thereof include a vinyl group, an allyl group, and a 3-butenyl group.

[0048] The alkynyl group is not particularly limited, and is preferably an alkynyl group having 2 to 18 carbon atoms, and more preferably an alkynyl group having 2 to 10 carbon atoms. Specific examples thereof include ethynyl and prop-2-yn-1-yl (propargyl).

[0049] The alkylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkyl group, and is preferably an alkylcarbonyl group having 2 to 18 carbon atoms, and more preferably an alkylcarbonyl group having 2 to 10 carbon atoms. Specific examples thereof include acetyl, propionyl, butyryl, isobutyryl, pivaloyl, hexanoyl, octanoyl, and cyclohexylcarbonyl groups.

[0050] The alkenylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkenyl group, and is preferably an alkenylcarbonyl group having 3 to 18 carbon atoms, and more preferably an alkenylcarbonyl group having 3 to 10 carbon atoms. Specific examples thereof include acryloyl, methacryloyl, and crotonoyl groups.

[0051] The alkynylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkynyl group, and 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. Specific examples include propioloyl and the like.

[0052] The weight average molecular weight (Mw) of the modified polyphenylene ether compound is not particularly limited. Specifically, it is preferably 500 to 5000, more preferably 800 to 4000, and further preferably 1000 to 3000. It should be noted that, here, the weight average molecular weight is any value obtained by measuring the molecular weight using a conventional method, and specifically, values ​​measured using gel permeation chromatography (GPC) can be cited. In addition, when the modified polyphenylene ether compound has a repeating unit represented by the formula (11) in the molecule, t is preferably a value such that the weight average molecular weight of the modified polyphenylene ether compound is within the above range. Specifically, t is preferably 1 to 50.

[0053] If the weight average molecular weight of the modified polyphenylene ether compound is within the above range, the modified polyphenylene ether compound not only has the excellent low dielectric properties of polyphenylene ether, but also has better heat resistance and excellent formability. It is believed that this is based on the following reasons. In conventional polyphenylene ethers, if the weight average molecular weight is within the above range, the molecular weight is relatively low, so there is a tendency for the heat resistance of the cured product to decrease. In this regard, it is believed that since the modified polyphenylene ether compound involved in the present embodiment has more than one unsaturated double bond at the end, the cured product can obtain sufficiently high heat resistance. In addition, it is believed that if the weight average molecular weight of the modified polyphenylene ether compound is within the above range, the molecular weight is relatively low, so the formability is also excellent. Therefore, it is believed that the modified polyphenylene ether compound can obtain not only better heat resistance of the cured product, but also excellent formability.

[0054] The average number of the substituents (the number of terminal functional groups) possessed by each molecule of the modified polyphenylene ether compound at the molecular end is not particularly limited. Specifically, it is preferably 1 to 5, more preferably 1 to 3, and further 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. In addition, if the number of terminal functional groups is too large, the reactivity becomes too high, and there is a risk of undesirable conditions such as reduced storage stability of the resin composition or reduced fluidity of the resin composition. That is, if the modified polyphenylene ether compound is used, problems with formability may arise due to insufficient fluidity, for example, forming defects such as voids may occur during multilayer forming, and it is difficult to obtain a printed wiring board with high reliability.

[0055] It should be noted that the number of terminal functional groups of the modified polyphenylene ether compound can be listed as: a numerical value representing the average value of the substituents present in each molecule of all modified polyphenylene ether compounds in 1 mol of the modified polyphenylene ether compound, etc. The number of terminal functional groups can be determined, for example, by measuring the number of hydroxyl groups remaining in the obtained modified polyphenylene ether compound and calculating the reduction compared with the number of hydroxyl groups of the polyphenylene ether before modification. The reduction compared with the number of hydroxyl groups of the polyphenylene ether before modification is the number of terminal functional groups. In addition, the method for determining the number of hydroxyl groups remaining in the modified polyphenylene ether compound can be obtained by adding a quaternary ammonium salt (tetraethylammonium hydroxide) associated with the hydroxyl group to a solution of the modified polyphenylene ether compound and measuring the UV absorbance of the mixed solution.

[0056] The intrinsic viscosity of the modified polyphenylene ether compound is not particularly limited. Specifically, it can be 0.03 to 0.12 dl / g, but preferably 0.04 to 0.11 dl / g, and more preferably 0.06 to 0.095 dl / g. If the intrinsic viscosity is too low, there is a tendency for the molecular weight to be low, and there is a tendency for low dielectric properties such as low dielectric constant and low dielectric loss factor to be difficult to obtain. In addition, if the intrinsic viscosity is too high, there is a tendency for the viscosity to be high, it is difficult to obtain sufficient fluidity, and the formability of the cured product to be reduced. Therefore, as long as the intrinsic viscosity of the modified polyphenylene ether compound is within the above range, excellent heat resistance and formability of the cured product can be achieved.

[0057] It should be noted that the intrinsic viscosity here refers to the intrinsic viscosity measured in dichloromethane at 25°C, and more specifically, for example, is a value obtained by measuring a 0.18 g / 45 ml dichloromethane solution (liquid temperature 25°C) using a viscometer. Examples of such a viscometer include AVS500 Visco System manufactured by Schott.

[0058] Examples of the modified polyphenylene ether compound include a modified polyphenylene ether compound represented by the following formula (12) and a modified polyphenylene ether compound represented by the following formula (13). In addition, as the modified polyphenylene ether compound, these modified polyphenylene ether compounds may be used alone or in combination.

[0059]

[0060] In formula (12) and formula (13), R9 to R 16 and R 17 ~R 24Each 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. X1 and X2 each independently represent a substituent having a carbon-carbon unsaturated double bond. A and B represent the repeating unit shown in the following formula (14) and the following formula (15), respectively. In addition, in formula (13), Y represents a straight-chain, branched, or cyclic hydrocarbon having a carbon number of less than 20.

[0061]

[0062] In formula (14) and formula (15), m and n represent 0 to 20 respectively. 25 ~R 28 and R 29 ~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.

[0063] The modified polyphenylene ether compound represented by the formula (12) and the modified polyphenylene ether compound represented by the formula (13) are not particularly limited as long as they satisfy the above-mentioned constitution. Specifically, in the formula (12) and the formula (13), as described above, R9 to R 16 and R 17 ~R 24 Each is independent. That is, R9~R 16 and R 17 ~R 24 They may be the same group or different groups. 16 and R 17 ~R 24 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 them, a hydrogen atom and an alkyl group are preferred.

[0064] In formula (14) and formula (15), m and n are each preferably 0 to 20 as described above. In addition, regarding m and n, the total value of m and n is preferably a numerical value of 1 to 30. Therefore, it is more preferable that m represents 0 to 20, n represents 0 to 20, and the total value of m and n represents 1 to 30. In addition, R 25 ~R 28 and R 29 ~R 32 are independent of each other. That is, R 25 ~R 28 and R 29 ~R 32 They may be the same group or different groups. 25 ~R 28 and R 29 ~R 32represents 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 them, a hydrogen atom and an alkyl group are preferred.

[0065] R9~R 32 The same as R5 to R8 in the above formula (11).

[0066] In the formula (13), as described above, Y is a linear, branched or cyclic hydrocarbon having a carbon number of not more than 20. Examples of Y include groups represented by the following formula (16).

[0067]

[0068] In the formula (16), R 33 and R 34 Each independently represents a hydrogen atom or an alkyl group. Examples of the alkyl group include a methyl group. In addition, examples of the group represented by formula (16) include a methylene group, a methylmethylene group, and a dimethylmethylene group, among which dimethylmethylene group is preferred.

[0069] In the formula (12) and the formula (13), X1 and X2 are each independently a substituent having a carbon-carbon unsaturated double bond. As the substituents X1 and X2, there is no particular limitation as long as they are substituents having a carbon-carbon unsaturated double bond. As the substituents X1 and X2, for example, substituents represented by the above formula (5) and substituents represented by the above formula (6) can be listed. It should be noted that in the modified polyphenylene ether compound represented by the formula (12) and the modified polyphenylene ether compound represented by the formula (13), X1 and X2 can be the same substituent or different substituents.

[0070] More specific examples of the modified polyphenylene ether compound represented by the formula (12) include a modified polyphenylene ether compound represented by the following formula (17).

[0071]

[0072] More specific examples of the modified polyphenylene ether compound represented by the formula (13) include a modified polyphenylene ether compound represented by the following formula (18) and a modified polyphenylene ether compound represented by the following formula (19).

[0073]

[0074] In the above formulae (17) to (19), m and n have the same meanings as m and n in the above formulae (14) and (15), and are 0 to 20, respectively. In addition, in the above formulae (17) and (18), R1 to R3, p, and Z are the same as R1 to R3, p, and Z in the above formula (5). In addition, in the above formulae (18) and (19), Y is the same as Y in the above formula (13). In addition, in the above formula (19), R4 is the same as R4 in the above formula (6).

[0075] The synthesis method of the modified polyphenylene ether compound used in the present embodiment is not particularly limited as long as it can synthesize a modified polyphenylene ether compound that is terminally modified using a substituent having a carbon-carbon unsaturated double bond. Specifically, there can be cited a method of reacting a polyphenylene ether with a compound bonded with a substituent having a carbon-carbon unsaturated double bond and a halogen atom.

[0076] Examples of the compound to which a substituent having a carbon-carbon unsaturated double bond and a halogen atom are bonded include, for example, compounds to which a substituent represented by the formula (5), (6), or (10) and a halogen atom are bonded. Specifically, the halogen atom includes a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom, and a chlorine atom is preferred. More specifically, examples of the compound to which a substituent having a carbon-carbon unsaturated double bond and a halogen atom are bonded include p-chloromethylstyrene, m-chloromethylstyrene, and the like.

[0077] The polyphenylene ether used as a raw material is not particularly limited as long as it is a polyphenylene ether that can eventually synthesize a specified modified polyphenylene ether compound. Specifically, it includes: a polyphenylene ether containing "2,6-dimethylphenol" and "at least one of a difunctional phenol and a trifunctional phenol", or a compound containing polyphenylene ethers such as poly(2,6-dimethyl-1,4-phenylene ether) as a main component, etc. In addition, the so-called difunctional phenol is a phenol compound having two phenolic hydroxyl groups in the molecule, for example, tetramethyl bisphenol A, etc. can be mentioned. In addition, the so-called trifunctional phenol is a phenol compound having three phenolic hydroxyl groups in the molecule.

[0078] The synthetic method of the modified polyphenylene ether compound can be exemplified by the above-mentioned method. Specifically, the polyphenylene ether as described above and the compound bonded with a substituent having a carbon-carbon unsaturated double bond and a halogen atom are dissolved in a solvent and stirred. Thus, the polyphenylene ether reacts with the compound bonded with a substituent having a carbon-carbon unsaturated double bond and a halogen atom to obtain the modified polyphenylene ether compound used in the present embodiment.

[0079] During the reaction, it is preferably carried out in the presence of an alkali metal hydroxide. It is believed that this reaction can be carried out well. It is believed that the reason is that the alkali metal hydroxide acts as a dehydrohalogenating agent, specifically, as a dehydrochlorination agent. That is, it is believed that the alkali metal hydroxide causes the hydrogen halide to be separated from the phenolic group of the polyphenylene ether and the compound bonded with a substituent having a carbon-carbon unsaturated double bond and a halogen atom, thereby, the substituent having a carbon-carbon unsaturated double bond replaces the hydrogen atom of the phenolic group of the polyphenylene ether and is bonded to the oxygen atom of the phenolic group.

[0080] The alkali metal hydroxide is not particularly limited as long as it can function as a dehalogenating agent, and examples thereof include sodium hydroxide, etc. The alkali metal hydroxide is generally used in the form of an aqueous solution, and specifically, is used as an aqueous sodium hydroxide solution.

[0081] Reaction conditions such as reaction time and reaction temperature vary depending on the compound bonded with a substituent having a carbon-carbon unsaturated double bond and a halogen atom, and are not particularly limited as long as they are conditions that allow the above reaction to proceed well. Specifically, the reaction temperature is preferably room temperature to 100° C., more preferably 30 to 100° C. In addition, the reaction time is preferably 0.5 to 20 hours, more preferably 0.5 to 10 hours.

[0082] The solvent used in the reaction is not particularly limited as long as it can dissolve the polyphenylene ether and the compound having a substituent having a carbon-carbon unsaturated double bond and a halogen atom bonded thereto and does not hinder the reaction of the polyphenylene ether and the compound having a substituent having a carbon-carbon unsaturated double bond and a halogen atom bonded thereto. Specifically, toluene and the like can be cited.

[0083] It is preferred that the above reaction is carried out in the presence of not only alkali metal hydroxide but also phase transfer catalyst. That is, it is preferred that the above reaction is carried out in the presence of alkali metal hydroxide and phase transfer catalyst. It is believed that the above reaction can be carried out better in this way. It is believed that this is based on the following reasons. It is believed that: this is because the phase transfer catalyst is a catalyst, that is, it has the function of introducing alkali metal hydroxide, and is soluble in the polar solvent phase of water and the non-polar solvent phase of organic solvent, and can move between these phases. Specifically, it is believed that: when using sodium hydroxide aqueous solution as alkali metal hydroxide, and using organic solvents such as toluene that are incompatible with water as solvent, even if sodium hydroxide aqueous solution is added dropwise to the solvent for reaction, the solvent and sodium hydroxide aqueous solution will also be separated, and sodium hydroxide is difficult to migrate to the solvent. So, it is believed that: the sodium hydroxide aqueous solution added as alkali metal hydroxide is difficult to contribute to the promotion of reaction. In contrast, it is believed that: if the reaction is carried out in the presence of alkali metal hydroxide and phase transfer catalyst, the alkali metal hydroxide will migrate to the solvent under the state of being introduced into the phase transfer catalyst, and the sodium hydroxide aqueous solution becomes easy to contribute to the promotion of reaction. Therefore, it is considered that the above reaction will proceed more effectively if the reaction is carried out in the presence of an alkali metal hydroxide and a phase transfer catalyst.

[0084] The phase transfer catalyst is not particularly limited, and examples thereof include quaternary ammonium salts such as tetra-n-butylammonium bromide.

[0085] The resin composition used in the present embodiment preferably contains the modified polyphenylene ether compound obtained as described above as the modified polyphenylene ether compound.

[0086] (Free Radical Compounds)

[0087] The free radical compound used in the present embodiment is not particularly limited as long as it is a free radical compound having at least one of the structures shown in the above-mentioned formulas (1) to (4). It is believed that by containing the free radical compound, the resin composition of the present embodiment has the characteristics of low dielectric properties, heat resistance, etc., and can also exert excellent formability (formability that can be filled into circuit patterns). In addition, it is believed that a cured product that can well maintain low dielectric properties even after heat treatment or water absorption treatment can be obtained.

[0088] Preferably, the radical compound of the present embodiment includes at least one compound selected from the group consisting of compounds represented by the following formulae (7) to (9).

[0089]

[0090] In the above formula (7) and formula (8), X A and X BEach independently represents a hydrogen atom, an amino group, a cyano group, a hydroxyl group, an isothiocyanate group, a methoxy group, a carboxyl group, a carbonyl group, an amide group, a benzoyloxy group, or an ether bond.

[0091] More specific examples thereof include 4-acetamido, 4-glycidyloxy, 4-benzoyloxy, 4-(2-iodoacetamido)yl, 4-[2-[2-(4-iodophenoxy)ethoxy]carbonyl]benzoyloxy, 4-methacryloyloxy, 4-oxy, and 4-propargyloxy.

[0092] In addition, in the formula (9), X C represents an alkylene group, an aromatic structure, a carbonyl group, an amide group or an ether bond.

[0093] The alkylene group may have a linear structure, a side chain structure and / or a cyclic structure, and the length of the linear chain and the side chain is not particularly limited. If the carbon number is too large, the solubility of the resin component in the solvent may sometimes be reduced, so, for example, the carbon number is preferably 16 or less, and the carbon number is particularly preferably about 8 or less.

[0094] When the alkylene group has a cyclic structure, for example, a seven-membered ring, a six-membered ring, a five-membered ring structure, etc. are mentioned.

[0095] In addition, examples of the aromatic structure include a phenyl group, a pyrrolyl group, a thiazolyl group, and the like.

[0096] More specific free radical compounds preferably used in the present embodiment include 4-amino-2,2,6,6-tetramethylpiperidinyl 1-oxyl free radical, 4-acetamido-2,2,6,6-tetramethylpiperidinyl 1-oxyl free radical, 4-amino-2,2,6,6-tetramethylpiperidinyl 1-oxyl free radical, 4-carboxy-2,2,6,6-tetramethylpiperidinyl 1-oxyl free radical, 4-cyano-2,2,6,6-tetramethylpiperidinyl 1-oxyl free radical, 4-glycidyloxy-2,2,6,6-tetramethylpiperidinyl 1-oxyl free radical, 4 -hydroxy-2,2,6,6-tetramethylpiperidinyl 1-oxyl free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidinyl 1-oxybenzoate free radical, 4-isothiocyanate-2,2,6,6-tetramethylpiperidinyl 1-oxyl free radical, 4-(2-iodoacetamido)-2,2,6,6-tetramethylpiperidinyl 1-oxyl free radical, 4-[2-[2-(4-iodophenoxy)ethoxy]carbonyl]benzoyloxy-2,2,6,6-tetramethylpiperidinyl-1-oxyl free radical, 4-methoxy-2,2,6,6-tetramethylpiperidinyl 1-oxyl free radical, 4-Methacryloyloxy-2,2,6,6-tetramethylpiperidinyl 1-oxyl free radical, 4-oxo-2,2,6,6-tetramethylpiperidinyl 1-oxyl free radical, 4-oxo-2,2,6,6-tetramethylpiperidinyl 1-oxyl free radical, 2,2,6,6-tetramethylpiperidinyl 1-oxyl free radical, 2,2,6,6-tetramethylpiperidinyl 1-oxyl free radical, 2,2,6,6-tetramethyl-4-(2-propynyloxy)piperidinyl 1-oxyl free radical, 2,2,6,6-tetramethylpiperidinyl 1-oxyl free radical, 4,5-dihydroxy-4,4,5,5-tetramethyl-2-phenyl-1H-imidazol-1-yloxy 1-oxyl free radical, 2-(4-nitrophenyl)-4,4,5,5-tetramethylimidazoline-3-oxide-1-oxyl free radical, 2-(14-carboxytetradecyl)-2-ethyl-4,4-dimethyl-3-oxazolidinyloxy free radical, 1,1-diphenyl-2-picrylhydrazyl free radical, and the like.

[0097] Various radical compounds are listed above, and these may be used alone or in combination of two or more.

[0098] The radical compound described above in the present embodiment can be a commercially available radical compound, which can be obtained from, for example, Tokyo Chemical Industry Co., Ltd.

[0099] (Curing agent)

[0100] The resin composition of the present embodiment preferably further contains a curing agent.

[0101] As the curing agent, there is no particular limitation as long as it is a curing agent that can react with the modified polyphenylene ether compound to cure the resin composition containing the modified polyphenylene ether compound. As for the curing agent, there can be cited curing agents having at least one functional group in the molecule that contributes to the reaction with the modified polyphenylene ether compound, etc. As the curing agent, for example, styrene, styrene derivatives, compounds having an acryloyl group in the molecule, compounds having a methacryloyl group in the molecule, compounds having a vinyl group in the molecule, compounds having an allyl group in the molecule, compounds having a maleimide group in the molecule, compounds having a acenaphthylene structure in the molecule, and isocyanurate compounds having an isocyanurate group in the molecule, etc. can be cited.

[0102] Examples of the styrene derivatives include bromostyrene and dibromostyrene.

[0103] The compound having an acryloyl group in the molecule is an acrylate compound. Examples of the acrylate compound include a monofunctional acrylate compound having one acryloyl group in the molecule and a multifunctional acrylate compound having two or more acryloyl groups in the molecule. Examples of the monofunctional acrylate compound include methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate. Examples of the multifunctional acrylate compound include tricyclodecane dimethanol diacrylate.

[0104] The compound having a methacryloyl group in the molecule is a methacrylate compound. Examples of the methacrylate compound include a monofunctional methacrylate compound having one methacryloyl group in the molecule and a polyfunctional methacrylate compound having two or more methacryloyl groups in the molecule. Examples of the monofunctional methacrylate compound include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate. Examples of the polyfunctional methacrylate compound include tricyclodecane dimethanol dimethacrylate.

[0105] The compound having a vinyl group in the molecule is a vinyl compound. Examples of the vinyl compound include a monofunctional vinyl compound having one vinyl group in the molecule (monovinyl compound) and a polyfunctional vinyl compound having two or more vinyl groups in the molecule. Examples of the polyfunctional vinyl compound include divinylbenzene and polybutadiene.

[0106] The compound having an allyl group in the molecule is an allyl compound. Examples of the allyl compound include a monofunctional allyl compound having one allyl group in the molecule and a polyfunctional allyl compound having two or more allyl groups in the molecule. Examples of the polyfunctional allyl compound include diallyl phthalate (DAP) and the like.

[0107] The compound having a maleimide group in the molecule is a maleimide compound. Examples of the maleimide compound include: a monofunctional maleimide compound having one maleimide group in the molecule, a polyfunctional maleimide compound having two or more maleimide groups in the molecule, and a modified maleimide compound. Examples of the modified maleimide compound include: a modified maleimide compound in which a part of the molecule is modified by an amine compound, a modified maleimide compound in which a part of the molecule is modified by an organosilicon compound, and a modified maleimide compound in which a part of the molecule is modified by an amine compound and an organosilicon compound.

[0108] The compound having an acenaphthylene structure in the molecule is an acenaphthylene compound. Examples of the acenaphthylene compound include acenaphthylene, alkyl acenaphthylenes, halogenated acenaphthylenes, and phenyl acenaphthylenes. Examples of the alkyl acenaphthylenes include 1-methyl acenaphthylene, 3-methyl acenaphthylene, 4-methyl acenaphthylene, 5-methyl acenaphthylene, 1-ethyl acenaphthylene, 3-ethyl acenaphthylene, 4-ethyl acenaphthylene, and 5-ethyl acenaphthylene. Examples of the halogenated acenaphthylenes include 1-chloro acenaphthylene, 3-chloro acenaphthylene, 4-chloro acenaphthylene, 5-chloro acenaphthylene, 1-bromo acenaphthylene, 3-bromo acenaphthylene, 4-bromo acenaphthylene, and 5-bromo acenaphthylene. Examples of the phenylacenaphthylene include 1-phenylacenaphthylene, 3-phenylacenaphthylene, 4-phenylacenaphthylene, 5-phenylacenaphthylene, etc. The acenaphthylene compound may be a monofunctional acenaphthylene compound having one acenaphthylene structure in the molecule as described above, or a polyfunctional acenaphthylene compound having two or more acenaphthylene structures in the molecule.

[0109] The compound having an isocyanurate group in the molecule is an isocyanurate compound. Examples of the isocyanurate compound include compounds further having an alkenyl group in the molecule (alkenyl isocyanurate compounds), such as triallyl isocyanurate (TALC) and the like.

[0110] As for the curing agent, among the above, preferred are, for example: a multifunctional acrylate compound having two or more acryloyl groups in the molecule, a multifunctional methacrylate compound having two or more methacryloyl groups in the molecule, a multifunctional vinyl compound having two or more vinyl groups in the molecule, a styrene derivative, an allyl compound having an allyl group in the molecule, a maleimide compound having a maleimide group in the molecule, an acenaphthylene compound having an acenaphthylene structure in the molecule, and an isocyanurate compound having an isocyanurate group in the molecule.

[0111] The curing agent may be used alone or in combination of two or more.

[0112] The weight average molecular weight of the curing agent is preferably 100 to 5000, more preferably 100 to 4000, and further preferably 100 to 3000. If the weight average molecular weight of the curing agent is too low, there is a risk that the curing agent may easily volatilize from the compounding component system of the resin composition. In addition, if the weight average molecular weight of the curing agent is too high, there is a risk that the viscosity of the varnish of the resin composition or the melt viscosity during heating and forming becomes too high. Therefore, if the weight average molecular weight of the curing agent is within this range, a resin composition with better heat resistance of the cured product can be obtained. It is believed that the reason is that the resin composition containing the modified polyphenylene ether compound can be well cured by reacting with the modified polyphenylene ether compound. It should be noted that, here, the weight average molecular weight is any value obtained by measuring the weight average molecular weight by a conventional molecular weight measurement method, and specifically, the value measured by gel permeation chromatography (GPC) can be cited.

[0113] Regarding the curing agent, the average number of functional groups (functional group number) in each molecule of the curing agent that contributes to the reaction with the modified polyphenylene ether compound varies according to the weight average molecular weight of the curing agent, and is preferably 1 to 20, and more preferably 2 to 18. If the number of functional groups is too small, it tends to be difficult to obtain a cured product with sufficient heat resistance. In addition, if the number of functional groups is too large, the reactivity becomes too high, and there is a risk of undesirable conditions such as reduced storage of the resin composition or reduced fluidity of the resin composition.

[0114] (Reaction initiator)

[0115] The resin combination that the present embodiment is related to can also contain reaction initiator (initiator). Even if the resin combination is formed by the modified polyphenylene ether compound and the curing agent, it can also carry out curing reaction. In addition, it is only the modified polyphenylene ether compound that can also carry out curing reaction. However, according to process conditions, it is sometimes difficult to raise the temperature until curing is carried out, so reaction initiator can also be added.

[0116] The reaction initiator is not particularly limited as long as it can promote the curing reaction of the modified polyphenylene ether compound (or the curing agent when the curing agent is included), and specific examples thereof include metal oxides, azo compounds, and organic peroxides.

[0117] Specific examples of the metal oxide include carboxylic acid metal salts and the like.

[0118] Examples of the organic peroxide include a,a′-di(tert-butylperoxy)diisopropylbenzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne, benzoyl peroxide, 3,3′,5,5′-tetramethyl-1,4-diphenolquinone, chloranil, 2,4,6-tri-tert-butylphenoxy, tert-butylperoxyisopropyl monocarbonate, and azobisisobutyronitrile.

[0119] Specific examples of the azo compound include 2,2′-azobis(2,4,4-trimethylpentane), 2,2′-azobis(N-butyl-2-methylpropionamide), and 2,2′-azobis(2-methylbutyronitrile).

[0120] Wherein, preferred reaction initiator is 2,2'-azobis(2,4,4-trimethylpentane), 2,2'-azobis(N-butyl-2-methylpropionamide) etc.These reaction initiators have little influence on dielectric properties.In addition, it is because there is the following advantage: because the reaction starting temperature is relatively high, therefore when the prepreg is dried, etc., it is not necessary to solidify the moment and can suppress the promotion of curing reaction, and can suppress the preservation property reduction of the resin combination.

[0121] The above-mentioned reaction initiators may be used alone or in combination of two or more.

[0122] (Inorganic filler)

[0123] The resin composition involved in the present embodiment can also contain fillers such as inorganic fillers. As fillers, materials added to suppress the thermal expansion of the cured product of the resin composition and improve flame retardancy can be cited, without particular limitation. In addition, by containing fillers, heat resistance and flame retardancy can be further improved. As fillers, specifically, metal oxides such as silicon dioxide, aluminum oxide, titanium oxide and mica, metal hydroxides such as aluminum hydroxide, magnesium hydroxide, talc, aluminum borate, barium sulfate and calcium carbonate can be cited. In addition, as fillers, silicon dioxide, mica and talc are preferably used, and spherical silicon dioxide is more preferably used. In addition, a filler can be used alone or in combination of two or more. In addition, as a filler, it can be used directly, or a filler surface-treated with the silane coupling agent can be used.

[0124] In addition, as an inorganic filler, it is also preferred to use silicon dioxide, in which the ratio of the number of Si atoms contained in the silanol group to the total number of Si atoms is 3% or less. It is believed that: by making the resin composition of the present embodiment contain silicon dioxide with few silanol groups as described above as an inorganic filler, it is further possible to obtain a resin composition that can better maintain a cured product with low dielectric properties even after heat treatment. Regarding the silicon dioxide, the ratio of the number of Si atoms contained in the silanol group to the total number of Si atoms is 3% or less, and is preferably 2.5% or less, and more preferably 2% or less. In addition, the lower the ratio, the better, but in fact the limit is about 0.1%. Therefore, the ratio is preferably 0.1 to 3%.

[0125] The determination of the ratio of the number of Si atoms contained in the silanol groups in the silicon dioxide to the total number of Si atoms is not particularly limited as long as the ratio of the number of Si atoms contained in the silanol groups (Si-OH) contained in the silicon dioxide to the total number of Si atoms contained in the silicon dioxide can be determined. For example, the determination can be performed by obtaining a spectrum of silicon dioxide by solid-state 29Si-NMR measurement, etc.

[0126] (Content)

[0127] The content of the free radical compound is preferably 0.01 to 0.4 parts by mass, more preferably 0.05 to 0.3 parts by mass, and further preferably 0.1 to 0.2 parts by mass, relative to 100 parts by mass of the total of the modified polyphenylene ether compound and the curing agent in the resin composition. It is believed that if the content of the free radical compound is within the above range, a resin composition having low dielectric properties and high heat resistance and better maintaining low dielectric properties even after heat treatment and / or water absorption treatment can be obtained more reliably, and excellent in formability.

[0128] The content of the modified polyphenylene ether compound is preferably 10 to 95 parts by mass, more preferably 15 to 90 parts by mass, and further preferably 20 to 90 parts by mass, relative to 100 parts by mass of the resin component (organic component) in the resin composition. That is, the content of the modified polyphenylene ether compound is preferably 10 to 95% by mass relative to the components other than the inorganic filler in the resin composition.

[0129] The resin composition may contain the curing agent as described above. When the resin composition contains the curing agent, for example, the content of the curing agent is preferably 5 to 50 parts by mass, more preferably 10 to 50 parts by mass, relative to 100 parts by mass of the resin component (organic component) in the resin composition. In addition, the content of the curing agent is preferably 5 to 50 parts by mass, more preferably 10 to 50 parts by mass, relative to 100 parts by mass of the total of the modified polyphenylene ether compound and the curing agent.

[0130] When the contents of the modified polyphenylene ether compound and the curing agent are within the above ranges, a resin composition having a cured product having better heat resistance can be obtained. The reason for this is considered to be that the curing reaction between the polymer and the curing agent proceeds well.

[0131] In the case where the resin composition of the present embodiment includes the reaction initiator, its content is not particularly limited, for example, relative to the total mass of 100 parts by mass of the polymer, the curing agent and the modified polyphenylene ether compound, preferably 0.5 to 8.0 parts by mass, more preferably 0.5 to 5.0 parts by mass, and further preferably 0.5 to 2.0 parts by mass. If the content of the reaction initiator is too little, there is a tendency that the curing reaction of the modified polyphenylene ether compound and the curing agent cannot start well. In addition, if the content of the initiator is too much, the dielectric loss factor of the cured product of the obtained prepreg becomes large, and there is a tendency to be difficult to exert excellent low dielectric properties. Therefore, if the content of the reaction initiator is within the above range, a cured product of a prepreg with excellent low dielectric properties can be obtained.

[0132] When the resin composition of the present embodiment includes the reaction initiator, the ratio of the radical compound to the reaction initiator in the resin composition is preferably about 0.005:1.0 to 0.2:1.0, more preferably about 0.01:1.0 to 0.2:1.0, and even more preferably about 0.1:1.0 to 0.2:1.0. It is believed that the effect of the present invention can be more reliably obtained in this way.

[0133] Furthermore, when the resin composition of the present embodiment contains an inorganic filler, the content rate (filler content) thereof is preferably 30 to 270% by mass, more preferably 50 to 250% by mass, based on the resin composition.

[0134] (Other ingredients)

[0135] The resin combination that the present embodiment is related to can also comprise the composition (other components) except the above-mentioned composition as required within the scope of not damaging the effect of the present invention.Other components contained by the resin combination that the present embodiment is related to can further contain the additives such as reaction accelerator, catalyst, dispersant, leveling agent, silane coupling agent, flame retardant, defoamer, antioxidant, heat stabilizer, antistatic agent, ultraviolet light absorber, dye or pigment and lubricant etc.In addition, in the resin combination, except containing the modified polyphenylene ether compound, the curing agent, the polymer, the thermosetting resins such as polyphenylene ether, epoxy resin can also be contained.

[0136] As described above, the resin composition involved in the present embodiment may contain a flame retardant. By containing a flame retardant, the flame retardancy of the cured product of the resin composition can be improved. The flame retardant is not particularly limited. Specifically, in the field of using halogen-based flame retardants such as bromine-based flame retardants, preferred examples include: ethylenedipentabromobenzene (ethylenedipentabromobenzene), ethylenebistetrabromoimide (ethylenebistetrabromoimide), tetradecabromodiphenyl ether, and tetradecabromodiphenyloxybenzene having a melting point of more than 300°C. It is believed that by using a halogen-based flame retardant, the detachment of halogen at high temperatures can be suppressed, and the reduction in heat resistance can be suppressed. In addition, in the field requiring halogen-free, phosphorus-containing flame retardants and the like can be cited. Specifically, examples include: phosphate ester-based flame retardants, phosphazene-based flame retardants, bisdiphenylphosphine-based flame retardants, and phosphinate-based flame retardants. As a specific example of phosphate ester flame retardants, condensed phosphate esters of dixylyl phosphate can be listed. As a specific example of phosphazene flame retardants, phenoxyphosphazene can be listed. As a specific example of bisdiphenylphosphine-based flame retardants, xylene bis(diphenylphosphine oxide) can be listed. As a specific example of hypophosphite flame retardants, for example, hypophosphite metal salts of dialkyl hypophosphite aluminum salts can be listed. As the flame retardant, each of the exemplified flame retardants can be used alone, or two or more can be used in combination.

[0137] (Manufacturing method)

[0138] The method for producing the resin composition is not particularly limited, and examples thereof include a method of mixing the modified polyphenylene ether compound and the free radical compound, and other components added as needed, etc. Specifically, in the case of obtaining a varnish-like composition containing an organic solvent, the method described in the description of the prepreg described later, etc. can be cited.

[0139] The resin composition of this embodiment preferably has T1 / T2 greater than 1.0 and less than 10.0, wherein T2 represents the lowest melt viscosity and T1 represents the melt viscosity at a temperature 10°C higher than the lowest melt viscosity. It is believed that this also has the advantages of low viscosity and easy expansion of the resin composition. It is particularly preferred that T1 / T2 is greater than 1.0 and less than 5.0, and it is further preferred that T1 / T2 is greater than 1.0 and less than 1.7.

[0140] In addition, it is preferred that T2 is 12000 (poise) or less, and T1 is 15000 (poise) or less. This is because it is believed that the resin composition is easily filled into the pattern, and the moldability is improved. In addition, it is preferred that T2 is 4000 (poise) or less, and T1 is 5000 (poise) or less, and it is particularly preferred that T2 is 1300 (poise) or less, and T1 is 1520 (poise) or less.

[0141] Furthermore, in the cured product of the resin composition of the present embodiment, the dielectric loss tangent (10 GHz) is preferably 0.0028 or less, and more preferably 0.0026 or less.

[0142] In addition, referring to JIS C 6481 (1996), when the cured product of the resin composition of the present embodiment is subjected to moisture absorption treatment (treated at a temperature of 85° C. and a humidity of 85% for 120 hours), and the difference between the dielectric loss factor of the cured product before the treatment is measured, it is preferred that (dielectric loss factor after moisture absorption treatment)-(dielectric loss factor before moisture absorption treatment) is 0.0006 or less, and more preferably 0.0004 or less.

[0143] In addition, when the cured product of the resin composition of the present embodiment is kept at 130° C. for 120 hours (heat treatment), and the difference between the dielectric loss factor of the cured product after the heat treatment (dielectric loss factor after the heat treatment) and the dielectric loss factor of the cured product before the treatment is measured, it is preferred that (dielectric loss factor after the heat treatment)-(dielectric loss factor before the heat treatment) is 0.0012 or less. More preferably, it is 0.0010 or less.

[0144] Furthermore, by using the resin composition according to the present embodiment, a prepreg, a metal foil-clad laminate, a wiring board, a metal foil with resin, and a film with resin can be obtained as follows. In the following description, the reference numerals are: 1 prepreg; 2 resin composition or semi-cured product of the resin composition; 3 fibrous substrate; 11 metal foil-clad laminate; 12 insulating layer; 13 metal foil; 14 wiring; 21 wiring board; 31 metal foil with resin; 32, 42 resin layers; 41 film with resin; 43 supporting film.

[0145] [Prepreg]

[0146] Figure 1 This is a schematic cross-sectional view showing an example of the prepreg 1 according to the embodiment of the present invention.

[0147] like Figure 1 As shown, the prepreg 1 according to the present embodiment comprises: the resin composition or the semi-cured product 2 of the resin composition; and a fibrous base material 3. The prepreg 1 comprises: the resin composition or the semi-cured product 2 of the resin composition; and the fibrous base material 3 present in the resin composition or the semi-cured product 2 of the resin composition.

[0148] It should be noted that, in the present embodiment, semi-cured material is the material of the state that resin combination is cured to the extent that can be further cured midway. That is, semi-cured material is the material of the state (B-stage) that makes resin combination semi-cured. For example, if resin combination is heated, initially viscosity slowly decreases, then begins to solidify, then begins to solidify, and viscosity slowly rises. In this case, as semi-cured, the state during the period from when viscosity begins to rise to before fully solidified etc. can be cited.

[0149] In addition, as a prepreg obtained by using the resin composition involved in the present embodiment, it can be a prepreg having a semi-cured product of the resin composition as described above, and it can also be a prepreg having an uncured resin composition. That is, it can be a prepreg having a semi-cured product of the resin composition (the resin composition in the B stage) and a fibrous substrate, and it can also be a prepreg having the resin composition before curing (the resin composition in the A stage) and a fibrous substrate. In addition, as the resin composition or the semi-cured product of the resin composition, it can be a substance obtained by drying or heat-drying the resin composition.

[0150] When manufacturing prepreg, the resin composition 2 is often prepared into a varnish state for use in order to penetrate into the substrate for forming the prepreg, that is, the fibrous substrate 3. That is, the resin composition 2 is usually mostly a resin varnish prepared into a varnish state. The varnish-like resin composition (resin varnish) can be prepared, for example, in the following manner.

[0151] First, each component soluble in an organic solvent in the composition of the resin combination is put into an organic solvent and dissolved. At this time, heating can be performed as required. Then, a component (for example, an inorganic filler material, etc.) insoluble in an organic solvent used as required is added, and a ball mill, a bead mill, a planetary mixer, a roller mill, etc. are used to disperse it into a specified dispersed state, so that a varnish-like resin combination can be modulated. As the organic solvent used herein, as long as it is an organic solvent that can dissolve the modified polyphenylene ether compound and the curing agent, etc. and will not hinder the curing reaction, it is not particularly limited. Specifically, for example toluene, methyl ethyl ketone (MEK), etc. can be cited.

[0152] The method for producing the prepreg is not particularly limited as long as the prepreg can be produced. Specifically, when producing the prepreg, the resin composition used in the present embodiment is often prepared in a varnish state as described above and used as a resin varnish.

[0153] As the fibrous substrate, specifically, for example, glass cloth, aramid cloth, polyester cloth, glass nonwoven fabric, aramid nonwoven fabric, polyester nonwoven fabric, pulp paper and cotton linter paper can be cited. It should be noted that if glass cloth is used, a laminate with excellent mechanical strength can be obtained, and glass cloth processed by flattening is particularly preferred. As a flattening process, specifically, for example, a method in which the yarn is compressed into a flat state by continuously pressing the glass cloth with a pressing roller at an appropriate pressure. It should be noted that the thickness of the commonly used fibrous substrate is, for example, greater than 0.01 mm and less than 0.3 mm.

[0154] The method for producing the prepreg is not particularly limited as long as the prepreg can be produced. Specifically, when producing the prepreg, the resin composition according to the present embodiment is often prepared in a varnish state as described above and used as a resin varnish.

[0155] As a method for manufacturing the prepreg 1, for example, a method of impregnating a resin composition 2 (e.g., a resin composition 2 modulated into a varnish state) into a fibrous substrate 3 and then drying the fibrous substrate 3 can be cited. The penetration of the resin composition 2 into the fibrous substrate 3 is performed by impregnation and coating, etc. The penetration can also be repeated multiple times as needed. Moreover, at this time, it is also possible to adjust the final desired composition and penetration amount by repeatedly impregnating with multiple resin compositions with different compositions or concentrations.

[0156] The fibrous substrate 3 impregnated with the resin composition (resin varnish) 2 is heated under the desired heating conditions (for example, heating at 80° C. or higher and 180° C. or lower for 1 minute or more and 10 minutes or less). By heating, a prepreg 1 in a pre-cured state (stage A) or a semi-cured state (stage B) can be obtained. It should be noted that by the heating, the organic solvent is volatilized from the resin varnish, and the organic solvent can be reduced or removed.

[0157] The prepreg having the resin composition or the semi-cured product of the resin composition according to the present embodiment is a prepreg which can appropriately obtain a cured product having low dielectric properties and high heat resistance and can well maintain low dielectric properties even after heat treatment and water absorption treatment. In addition, the prepreg has good formability and is excellent in filling properties into circuit patterns when used in wiring boards, etc.

[0158] [Metal foil laminate]

[0159] Figure 2 It is a schematic cross-sectional view showing an example of the metal foil-clad laminate 11 according to the embodiment of the present invention.

[0160] like Figure 2 As shown, the metal foil-clad laminate 11 comprises: Figure 1 The insulating layer 12 of the cured product of the prepreg 1 shown in the figure; and the metal foil 13 laminated together with the insulating layer 12. That is, the metal foil-clad laminate 11 comprises: the insulating layer 12 comprising the cured product of the resin composition; and the metal foil 13 arranged on the insulating layer 12. In addition, the insulating layer 12 can be formed by the cured product of the resin composition, and can also be formed by the cured product of the prepreg. In addition, the thickness of the metal foil 13 varies depending on the performance required of the wiring board finally obtained, and is not particularly limited. The thickness of the metal foil 13 can be appropriately set according to the required purpose, for example, preferably 0.2 to 70 μm. In addition, as the metal foil 13, for example, copper foil and aluminum foil can be listed. When the metal foil is thin, in order to improve the handling property, it can be a copper foil with a carrier having a peeling layer and a carrier.

[0161] As a method for manufacturing the metal foil-clad laminate 11, there is no particular limitation as long as the metal foil-clad laminate 11 can be manufactured. Specifically, a method for making a metal foil-clad laminate 11 using a prepreg 1 can be cited. As this method, it can be cited as follows: taking a piece of prepreg 1 or overlapping several pieces of prepreg 1, and then overlapping a metal foil 13 such as copper foil on the upper and lower surfaces or one side surface thereof, heating and pressurizing the metal foil 13 and the prepreg 1 to form a laminate 11 with metal foil on both sides or one side, etc. are prepared. That is, the metal foil-clad laminate 11 is obtained by stacking the metal foil 13 on the prepreg 1 and heating and pressurizing it. In addition, the heating and pressurizing conditions can be appropriately set according to the thickness of the metal foil-clad laminate 11 to be manufactured or the type of the composition of the prepreg 1. For example, the temperature can be set to 170 to 210°C, the pressure can be set to 3.5 to 4MPa, and the time can be set to 60 to 150 minutes. The metal foil-clad laminate may be produced without using a prepreg, for example, by applying a varnish-like resin composition on a metal foil, forming a layer containing the resin composition on the metal foil, and then heating and pressing the layer.

[0162] The metal-clad laminate having an insulating layer comprising a cured product of the resin composition according to the present embodiment is a metal-clad laminate having an insulating layer with low dielectric properties and high heat resistance, and which can well maintain low dielectric properties even after heat treatment and water absorption treatment. In addition, the laminate has good formability and excellent filling properties for circuit patterns when used in wiring boards, etc.

[0163] [Wiring board]

[0164] Figure 3 It is a schematic cross-sectional view showing an example of wiring board 21 according to the embodiment of the present invention.

[0165] like Figure 3 As shown, the wiring board 21 according to this embodiment includes: Figure 1 The insulating layer 12 used by curing the prepreg 1 shown in the figure; and the wiring 14 formed by laminating together with the insulating layer 12 and removing a part of the metal foil 13. That is, the wiring board 21 includes: the insulating layer 12 containing a cured product of the resin composition; and the wiring 14 provided on the insulating layer 12. In addition, the insulating layer 12 may be formed of the cured product of the resin composition, or may be formed of the cured product of the prepreg.

[0166] The method for manufacturing the wiring board 21 is not particularly limited as long as the wiring board 21 can be manufactured. Specifically, a method for manufacturing the wiring board 21 using the prepreg 1 can be cited. As this method, for example, a method for manufacturing a wiring board 21 in which wiring is provided as a circuit on the surface of the insulating layer 12 by etching the metal foil 13 on the surface of the metal foil laminate 11 manufactured as described above, etc. can be cited. That is, for the wiring board 21, a part of the metal foil 13 on the surface of the metal foil laminate 11 can be removed to form a circuit. In addition, as a method for forming a circuit, in addition to the above-mentioned method, a method for forming a circuit by a semi-additive process (SAP: Semi Additive Process) or a modified semi-additive process (MSAP: Modified Semi Additive Process) can be cited. The wiring board 21 has an insulating layer 12 with low dielectric properties and high heat resistance, and can well maintain low dielectric properties even after water absorption treatment.

[0167] The wiring board is a wiring board with low dielectric properties and high heat resistance and can well maintain the insulating layer of low dielectric properties even after heat treatment and water absorption treatment. In addition, the resin combination of the present embodiment has good formability and also plays a good filling property for the circuit pattern in the wiring board. Therefore, there is an advantage that can be used even in a wiring board with a narrow distance between conductor circuits (wiring). As long as the resin combination of the present embodiment is not particularly limited, it can also be well used in a wiring board with a conductor circuit pattern of at least a portion of the conductor circuit, for example, less than 50 μm.

[0168] In particular, the wiring board of the present embodiment may be a multilayer wiring board having two or more circuit layers, and as long as it is the resin composition of the present embodiment, it can be well used as an interlayer insulating material of the multilayer wiring board. Although not particularly limited, it may also be a multilayer wiring board having two or more circuit layers provided with a wiring pattern in which the distance between wirings is at least partially 50 μm or less. In addition, a wiring pattern in which the distance between wirings is at least partially 30 μm or less may also be provided.

[0169] In addition, the resin composition of the present embodiment is not particularly limited, and is preferably used in the insulating material of the insulating layer of a multilayer wiring board with a large number of circuit layers of 5 or more layers, and further, the circuit layers are 10 or more layers. In the manufacture of a multilayer wiring board with a large number of circuit layers of 5 or more layers, and further, 10 or more layers, the interlayer insulating material of the present embodiment can be used to stably bury each inner layer circuit in the multilayer step of forming each interlayer insulating layer, and excellent formability can be ensured. By ensuring excellent formability, when a multilayer wiring board with a large number of circuit layers of 5 or more layers, and further, 10 or more layers, is hygroscopic and subjected to high temperature treatment, isolation can be prevented between the inner layer circuit of the multilayer wiring board and the bonding surface of the interlayer insulating layer.

[0170] [Metal foil with resin]

[0171] Figure 4 It is a schematic cross-sectional view showing an example of the metal foil with resin 31 according to the present embodiment.

[0172] like Figure 4 As shown in the figure, the metal foil with resin 31 according to the present embodiment comprises: a resin layer 32 containing the resin composition or a semi-cured product of the resin composition; and a metal foil 13. The metal foil with resin 31 has the metal foil 13 on the surface of the resin layer 32. That is, the metal foil with resin 31 comprises: the resin layer 32; and the metal foil 13 laminated together with the resin layer 32. In addition, the metal foil with resin 31 may further comprise another layer between the resin layer 32 and the metal foil 13.

[0173] In addition, as the resin layer 32, it may include a semi-cured product of the resin composition as described above, and may also include an uncured resin composition. That is, the metal foil with resin 31 may be a metal foil with resin, which includes: a resin layer including a semi-cured product of the resin composition (the resin composition in the B stage); and a metal foil with resin, or may be a resin layer including the resin composition before curing (the resin composition in the A stage); and a metal foil with resin. In addition, as the resin layer, as long as it includes the resin composition or the semi-cured product of the resin composition, it may include or not include a fibrous substrate. In addition, as the resin composition or the semi-cured product of the resin composition, it may be a substance obtained by drying or heat-drying the resin composition. In addition, as the fibrous substrate, the same material as the fibrous substrate of the prepreg can be used.

[0174] As the metal foil, any metal foil used in metal foil-clad laminates can be used without limitation. Examples of the metal foil include copper foil and aluminum foil.

[0175] The metal foil with resin 31 and the film with resin 41 may be provided with a covering film etc. as required. By providing the covering film, it is possible to prevent the mixing of foreign matter etc. The covering film is not particularly limited, and examples thereof include polyolefin films, polyester films, polymethylpentene films, and films formed by providing a release agent layer on these films.

[0176] The method for manufacturing the metal foil 31 with resin is not particularly limited as long as the metal foil 31 with resin can be manufactured. As the method for manufacturing the metal foil 31 with resin, there can be cited a method of applying the above-mentioned varnish-like resin composition (resin varnish) on the metal foil 13 and heating it. For example, the varnish-like resin composition is applied to the metal foil 13 using a scraper. The applied resin composition is heated under conditions of, for example, 80°C to 180°C and 1 minute to 10 minutes. The heated resin composition is formed on the metal foil 13 as an uncured resin layer 32. It should be noted that by the heating, the organic solvent is volatilized from the resin varnish, and the organic solvent can be reduced or removed.

[0177] The metal foil with resin having a resin layer including the resin composition or the semi-cured product of the resin composition involved in the present embodiment is a metal foil with resin having low dielectric properties and high heat resistance and can well maintain a cured product with low dielectric properties even after heat treatment and water absorption treatment. In addition, the metal foil has good formability and is excellent in filling properties of circuit patterns when used in wiring boards, etc. For example, a multilayer wiring board can be manufactured by stacking on a wiring board.

[0178] [Film with resin]

[0179] Figure 5 It is a schematic cross-sectional view showing an example of the film 41 with resin according to the present embodiment.

[0180] like Figure 5 As shown in FIG. 1 , the film 41 with resin according to the present embodiment includes: a resin layer 42 including the resin composition or a semi-cured product of the resin composition; and a support film 43. The film 41 with resin includes: the resin layer 42; and the support film 43 laminated together with the resin layer 42. In addition, the film 41 with resin may further include another layer between the resin layer 42 and the support film 43.

[0181] In addition, as the resin layer 42, it may include a semi-cured product of the resin composition as described above, and may also include an uncured resin composition. That is, the film 41 with resin may be a film with resin including: a resin layer including a semi-cured product of the resin composition (the resin composition in the B stage); and a supporting film, or may be a film with resin including: a resin layer including the resin composition before curing (the resin composition in the A stage); and a supporting film. In addition, as the resin layer, as long as it includes the resin composition or the semi-cured product of the resin composition, it may include or not include a fibrous substrate. In addition, as the resin composition or the semi-cured product of the resin composition, it may be a substance obtained by drying or heat-drying the resin composition. In addition, as the fibrous substrate, the same material as the fibrous substrate of the prepreg can be used.

[0182] In addition, any supporting film used in a film with a resin can be used without limitation as the supporting film 43. Examples of the supporting film include electrically insulating films such as polyester films, polyethylene terephthalate (PET) films, polyimide films, polyoxalyl urea films, polyetheretherketone films, polyphenylene sulfide films, polyamide films, polycarbonate films, and polyarylate films.

[0183] The film 41 with resin may include a cover film etc. as needed. By including the cover film, it is possible to prevent the mixing of foreign matter etc. The cover film is not particularly limited, and examples thereof include polyolefin films, polyester films, and polymethylpentene films.

[0184] The supporting film and the cover film may be films subjected to surface treatment such as matte treatment, corona treatment, mold release treatment, and roughening treatment as required.

[0185] The method for manufacturing the film 41 with resin is not particularly limited as long as the film 41 with resin can be manufactured. The method for manufacturing the film 41 with resin can include, for example, a method of applying the above-mentioned varnish-like resin composition (resin varnish) on the support film 43 and heating it. For example, the varnish-like resin composition is applied to the support film 43 using a scraper. The applied resin composition is heated under conditions of, for example, 80°C to 180°C and 1 minute to 10 minutes. The heated resin composition is formed on the support film 43 as an uncured resin layer 42. It should be noted that by the heating, the organic solvent is volatilized from the resin varnish, and the organic solvent can be reduced or removed.

[0186] The film with resin having a resin layer of a semi-cured product of the resin composition or the resin composition involved in the present embodiment is a film with resin having low dielectric properties and high heat resistance and a cured product with low dielectric properties that can be properly obtained even after heat treatment and water absorption treatment. In addition, the film has good formability and is excellent in filling properties of circuit patterns when used in wiring boards, etc. For example, a multilayer wiring board can be manufactured by peeling off a supporting film after being stacked on a wiring board, or by peeling off a supporting film and stacking on a wiring board.

[0187] Hereinafter, the present invention will be further specifically described by way of examples; however, the scope of the present invention is not limited to these examples.

[0188] Example

[0189] [Examples 1 to 15 and Comparative Examples 1 to 5]

[0190] Each component used to prepare the resin composition in this example is described.

[0191] (PPE ingredients)

[0192] Modified PPE1: a modified polyphenylene ether in which the terminal hydroxyl group of the polyphenylene ether is modified with a methacryloyl group (represented by the above formula (19), wherein Y in the formula (19) is a dimethylmethylene group (represented by the formula (16), wherein R in the formula (16) is 33 and R 34 A modified polyphenylene ether compound having a methyl group, SA9000 manufactured by SABIC Innovative Plastics, with a weight average molecular weight of Mw2000 and 2 terminal functional groups)

[0193] Modified PPE2: A modified polyphenylene ether obtained by reacting polyphenylene ether with chloromethylstyrene. Specifically, the modified polyphenylene ether is obtained by the following reaction.

[0194] First, 200 g of polyphenylene ether (SA90 manufactured by SABIC Innovative Plastics, with 2 terminal hydroxyl groups and a weight average molecular weight of Mw1700), 30 g of a mixture of p-chloromethylstyrene and m-chloromethylstyrene in a mass ratio of 50:50 (chloromethylstyrene manufactured by Tokyo Chemical Industry Co., Ltd.: CMS), 1.227 g of tetra-n-butylammonium bromide as a phase transfer catalyst, and 400 g of toluene were placed in a 1-liter three-necked flask equipped with a temperature regulator, a stirring device, a cooling device, and a dropping funnel, and stirred. Then, stirring was performed until the polyphenylene ether, chloromethylstyrene, and tetra-n-butylammonium bromide were dissolved in toluene. At this time, heating was performed slowly, and finally heated until the liquid temperature reached 75°C. Then, an aqueous sodium hydroxide solution (20 g sodium hydroxide / 20 g water) as an alkali metal hydroxide was added dropwise to the solution over a period of 20 minutes. Subsequently, stirring was further performed at 75°C for 4 hours. Next, the contents of the flask were neutralized with 10% by mass hydrochloric acid, and a large amount of methanol was added. This caused a precipitate to form in the liquid in the flask. That is, the product contained in the reaction liquid in the flask was reprecipitated. Then, the precipitate was taken out by filtration, washed three times with a mixed solution of methanol and water at a mass ratio of 80:20, and dried at 80°C for 3 hours under reduced pressure.

[0195] The obtained solid was analyzed by 1H-NMR (400 MHz, CDCl3, TMS). As a result of NMR measurement, a peak derived from vinylbenzyl (vinylbenzyl) was confirmed at 5 to 7 ppm. It was thus confirmed that the obtained solid was a modified polyphenylene ether compound having a vinylbenzyl (vinylbenzyl) group as the substituent at the molecular end in the molecule. Specifically, it was confirmed to be a polyphenylene ether that was vinylbenzylated. The obtained modified polyphenylene ether compound is represented by the above formula (18) and Y is a dimethylmethylene group (represented by formula (16) and R in formula (16) 33 and R 34 A modified polyphenylene ether compound in which Z is a phenylene group, R1 to R3 are hydrogen atoms, n is 1, and p is 1.

[0196] Furthermore, the number of terminal functional groups of the modified polyphenylene ether was measured in the following manner.

[0197] First, the modified polyphenylene ether was accurately weighed. The weight at this time was set to X (mg). Then, the weighed modified polyphenylene ether was dissolved in 25 mL of dichloromethane, and 100 μL of 10% by mass tetraethylammonium hydroxide (TEAH) ethanol solution (TEAH: ethanol (volume ratio) = 15: 85) was added to the solution, and the absorbance (Abs) at 318 nm was measured using a UV spectrophotometer (UV-1600 manufactured by Shimadzu Corporation). Then, based on the measurement results, the number of terminal hydroxyl groups of the modified polyphenylene ether was calculated using the following formula.

[0198] Residual OH amount (μmol / g) = [(25×Abs) / (ε×OPL×X)]x10 6

[0199] Here, ε represents the absorption coefficient, which is 4700 L / mol·cm. In addition, OPL represents the unit optical path length, which is 1 cm.

[0200] In addition, the calculated residual OH amount (number of terminal hydroxyl groups) of the modified polyphenylene ether is almost zero, so it can be known that almost all hydroxyl groups of the polyphenylene ether before modification are modified. Therefore, it can be known that the reduction compared with the number of terminal hydroxyl groups of the polyphenylene ether before modification is the number of terminal hydroxyl groups of the polyphenylene ether before modification. In other words, it can be known that the number of terminal hydroxyl groups of the polyphenylene ether before modification is the number of terminal functional groups of the modified polyphenylene ether. In other words, the number of terminal functional groups is 2.

[0201] In addition, the intrinsic viscosity (IV) of the modified polyphenylene ether in dichloromethane at 25°C was measured. Specifically, the intrinsic viscosity (IV) of the modified polyphenylene ether was measured using a viscometer (AVS500 Visco System manufactured by Schott) for a 0.18g / 45ml dichloromethane solution (liquid temperature 25°C). As a result, the intrinsic viscosity (IV) of the modified polyphenylene ether was 0.086dl / g. In addition, the molecular weight distribution of the modified polyphenylene ether was measured using GPC. Then, the weight average molecular weight (Mw) was calculated based on the obtained molecular weight distribution. As a result, Mw was 2300.

[0202] (Curing agent)

[0203] Acenaphthylene: Acenaphthylene manufactured by JFE Chemical Corporation

[0204] Maleimide compound: N-phenyl monomaleimide manufactured by Nippon Shokubai Co., Ltd.

[0205] Isocyanurate compound: Triallyl isocyanurate (TAIC) manufactured by Mitsubishi Chemical Corporation

[0206] (Reaction initiator)

[0207] Azo initiator: "VR-110" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

[0208] Peroxide initiator: PBP (1,3-bis(tert-butylperoxyisopropyl)benzene; PERBUTYL P manufactured by NOF Corporation)

[0209] (Free Radical Compounds)

[0210] Radical compound 1: a radical compound represented by the following formula ("H0865" manufactured by Tokyo Chemical Industry Co., Ltd.)

[0211]

[0212] Radical compound 2: a radical compound represented by the following formula ("T3751" manufactured by Tokyo Chemical Industry Co., Ltd.)

[0213]

[0214] Radical compound 3: a radical compound represented by the following formula ("H0878" manufactured by Tokyo Chemical Industry Co., Ltd.)

[0215]

[0216] Radical compound 4: a radical compound represented by the following formula ("B5642" manufactured by Tokyo Chemical Industry Co., Ltd.)

[0217]

[0218] Radical compound 5: a radical compound represented by the following formula ("C1406" manufactured by Tokyo Chemical Industry Co., Ltd.)

[0219]

[0220] Radical compound 6: a radical compound represented by the following formula ("D4313" manufactured by Tokyo Chemical Industry Co., Ltd.)

[0221]

[0222] Radical compound 7: a radical compound represented by the following formula ("G0020" manufactured by Tokyo Chemical Industry Co., Ltd.)

[0223]

[0224] (Catechol compounds)

[0225] 4-tert-Butylcatechol (4-tert-Butylcatechol manufactured by Tokyo Chemical Industry Co., Ltd.)

[0226] (Inorganic filler)

[0227] Silica filler 1: "SC-2300SVJ" manufactured by Admatechs Company Limited (silica having a silanol group content of 4.0%)

[0228] Silica filler 2: "5SV-C5" manufactured by Yaduma Co., Ltd. (silica containing 1.0% silanol groups)

[0229] (Preparation method)

[0230] First, the above-mentioned components except the inorganic filler were added to toluene in the composition (mass parts) described in Table 1 and mixed so that the solid content concentration was 55 mass %. The mixture was stirred for 60 minutes. Then, the inorganic filler was added to the resulting liquid, and the filler was dispersed with a bead mill. By doing so, a varnish-like resin composition (varnish) was obtained.

[0231] [Melt viscosity]

[0232] 0.5 g of the semi-cured material in the powder state of the resin composition obtained by the above-mentioned prepreg was pressed into a granular state with a diameter of 1.0 cm and a height of 0.5 cm under a pressure of 2.8 MPa, and it was used as a test sample. The melting behavior of the test sample was measured using a Rheosol-G3000NT dynamic viscoelasticity measuring device. As a measurement condition, the sample temperature was heated at 4 degrees per minute, and the viscosity of the sample at this time was measured. Then, the temperature at which the measured value of the viscosity decreased the most during the heating process from the semi-cured state (stage B) to the cured state (stage C) was set as the minimum melt viscosity (T2).

[0233] [T1 / T2]

[0234] The melt viscosity when the temperature rises by 10°C from the minimum melt viscosity (T2) is set as T1, and T1 / T2 is calculated. T1 / T2 is an index for measuring the curing speed from the state of T2 (the state where the viscosity becomes the minimum) once the temperature rises. The smaller the value of T1 / T2, the slower the curing speed, which is considered to be one of the characteristics of a resin composition with high moldability.

[0235] Next, an evaluation substrate (cured product of the prepreg) was obtained as follows.

[0236] After the obtained varnish was impregnated into a fibrous substrate (glass cloth: 1078L, #1078 type, L glass manufactured by Asahi Kasei Corporation), it was heated and dried at 120°C for 3 minutes to prepare a prepreg. At this time, it was adjusted so that the content (resin content) of the components constituting the resin by the curing reaction relative to the prepreg was 67% by mass. Then, two sheets of each obtained prepreg were overlapped, heated and pressed for 2 hours at a temperature of 200°C and a pressure of 3MPa, thereby obtaining an evaluation substrate (cured product of the prepreg).

[0237] Next, an evaluation substrate (metal foil-clad laminate) was obtained as follows.

[0238] The varnish was impregnated into a fibrous substrate (glass cloth: GC1078L, #1078 type, L glass manufactured by Asahi Kasei Corporation) and then dried by heating at 110° C. for 2 minutes to prepare a prepreg. At this time, the content of the component constituting the resin by the curing reaction (resin content) was adjusted to 67% by mass relative to the prepreg.

[0239] Two sheets of each of the obtained prepregs were overlapped, and copper foil (FV-WS produced by Furukawa Electric Co., Ltd., with a thickness of 18 μm) was arranged on both sides as a pressurized body. The prepregs were heated and pressed at a temperature of 200°C and a pressure of 3 MPa for 2 hours to produce an evaluation substrate (metal foil-clad laminate) with copper foil bonded to the surfaces of both sides, i.e., a copper foil-clad laminate.

[0240] The evaluation substrates (cured products of prepregs and metal foil-clad laminates) prepared as described above were evaluated by the methods shown below.

[0241] [Formability]

[0242] A cured product with a residual copper rate of 80%, a line thickness of 35μm, and a copper pattern of 200mm×200mm on the lattice was prepared. A prepreg of 200mm×200mm was stacked on it. A copper foil of 250mm×250mm with a thickness of 35pm was stacked on it. They were clamped with metal plates with a thickness of about 3mm, and heated and pressurized with a lamination press under the conditions shown below. As a heating condition, the temperature was increased from 30 degrees to 200 degrees at a heating rate of 4 degrees per minute. As a pressurization condition, at the beginning of heating, the pressure applied to the prepreg was set to 1MPa, and then when the temperature reached 110°C, the pressure applied to the prepreg was set to 3MPa, thereby curing the prepreg.

[0243] As a result, the evaluation of "○" was given when there was no gap between the lattice pattern and the solidified product and it was filled, and the evaluation of "×" was given when there was a gap. The presence or absence of the gap was determined by removing the copper foil of the solidified product made by the lamination press and transmitting light from the other side to see whether a gap that looked whitish could be confirmed.

[0244] [Dielectric loss factor before moisture absorption treatment]

[0245] The dielectric loss tangent of the evaluation substrate (cured prepreg) at 10 GHz was measured by the cavity perturbation method. Specifically, the dielectric loss tangent of the evaluation substrate at 10 GHz was measured using a network analyzer (N5230A manufactured by Keysight Technologies).

[0246] [Dielectric loss factor after moisture absorption treatment]

[0247] With reference to JIS C 6481 (1996), the evaluation substrate used in the measurement of the dielectric loss factor before the moisture absorption treatment was subjected to moisture absorption treatment, and the dielectric loss factor of the evaluation substrate after the moisture absorption treatment (dielectric loss factor after moisture absorption) was measured by the same method as the measurement of the dielectric loss factor before the moisture absorption treatment. It should be noted that the moisture absorption treatment was performed as follows: that is, the evaluation substrate was treated in an environment of a temperature of 85° C. and a humidity of 85% for 120 hours, and then the moisture on the evaluation substrate was fully wiped off with a dry and clean cloth, and the measurement was performed.

[0248] [Change in dielectric loss factor (after moisture absorption treatment - before moisture absorption treatment)]

[0249] The difference between the dielectric loss factor after the moisture absorption treatment and the dielectric loss factor before the moisture absorption treatment (dielectric loss factor after the moisture absorption treatment - dielectric loss factor before the moisture absorption treatment) was calculated.

[0250] [Dielectric loss factor before heat treatment]

[0251] The dielectric loss tangent of the evaluation substrate at 10 GHz was measured by the cavity perturbation method. Specifically, the dielectric loss tangent of the evaluation substrate at 10 GHz was measured using a network analyzer (N5230A manufactured by Keysight Technologies).

[0252] [Dielectric loss factor after heat treatment]

[0253] The evaluation substrate used in the measurement of the dielectric loss tangent before the heat treatment was maintained at 130° C. for 120 hours (heat treatment), and the dielectric loss tangent of the evaluation substrate after the heat treatment (dielectric loss tangent after the heat treatment) was measured using the same method as the measurement of the dielectric loss tangent before the heat treatment.

[0254] [Change in dielectric loss factor (after heat treatment - before heat treatment)]

[0255] The difference between the dielectric loss tangent after the heat treatment and the dielectric loss tangent before the heat treatment (= dielectric loss tangent after the heat treatment - dielectric loss tangent before the heat treatment) was calculated.

[0256] [Glass transition temperature (DMA) (Tg)]

[0257] The Tg of the cured product was measured using a viscoelasticity spectrometer "DMS6100" manufactured by Seiko Instruments Inc. At this time, dynamic viscoelasticity measurement (DMA) was performed using a bending module at a frequency of 10 Hz, and the temperature at which tan δ showed a maximum when the temperature was raised from room temperature to 320°C at a heating rate of 5°C / min was defined as Tg.

[0258] Table 1 shows the results of the above-mentioned evaluations.

[0259]

[0260] (Inspection)

[0261] As can be seen from Table 1, it was confirmed that all Examples using the resin composition of the present invention can provide a resin composition that can produce a cured product having low dielectric properties and high heat resistance and is not easily affected by changes in the external environment, and has moldability applicable to laminated wiring boards.

[0262] On the other hand, in Comparative Examples 1 to 3 that do not contain a free radical compound, the low dielectric properties cannot be maintained due to the influence of changes in the external environment. In addition, in Comparative Example 1 that does not contain a free radical compound and a reaction initiator, since solidification begins quickly after the minimum melting, the formability is poor. Comparative Examples 2 and 3 are also similar to Comparative Example 1. Due to the effect of adding a reaction initiator, solidification progresses quickly after the minimum melting, resulting in poor formability.

[0263] This application is based on Japanese patent application No. 2019-177946 filed on September 27, 2019, and the contents are incorporated herein by reference.

[0264] In order to describe the present invention, the present invention has been appropriately and fully described above with reference to specific examples and drawings, etc., and through embodiments, but it should be recognized that those skilled in the art can easily change and / or improve the embodiments. Therefore, as long as the modified embodiments or improved embodiments implemented by those skilled in the art do not deviate from the protection scope of the claims recorded in the claims, the modified embodiments or improved embodiments can be interpreted as being included in the protection scope of the claims.

[0265] Industrial Applicability

[0266] The present invention has broad industrial applicability in the technical field related to electronic materials and various devices using the same.

Claims

1. A resin composition, characterized in that contain: A modified polyphenylene ether compound whose terminal is modified by a substituent having a carbon-carbon unsaturated double bond; Free radical compounds; as well as A resin composition of a curing agent, wherein The free radical compound has at least one free radical selected from the group consisting of the structures represented by the following formula (1), formula (2), formula (3) and formula (4) in the molecule. ,and The free radical compound comprises at least one compound selected from the group consisting of compounds represented by the following formulas (7) to (9), In formula (7) and formula (8), X A and X B Each independently represents an amino group, a cyano group, a hydroxyl group, an isothiocyanate group, a methoxy group, a carboxyl group, an amide group, or a benzoyloxy group. In formula (9), X C represents an alkylene group, an aromatic structure, a carbonyl group, or an ether bond, The curing agent contains at least one of a compound having an acenaphthylene structure in the molecule, a monofunctional maleimide compound having one maleimide group in the molecule, and a compound having an isocyanurate group in the molecule, and When the cured product of the resin composition is heat-treated, i.e., maintained at 130° C. for 120 hours, the difference between the dielectric loss tangent at 10 GHz after the heat treatment and the dielectric loss tangent at 10 GHz before the heat treatment (= the dielectric loss tangent at 10 GHz after the heat treatment - the dielectric loss tangent at 10 GHz before the heat treatment) is 0.0012 or less.

2. The resin composition according to claim 1, characterized in that In the modified polyphenylene ether compound, the substituent includes at least one selected from the group represented by the following formula (5) and formula (6): In formula (5), p represents an integer of 0 to 10, Z represents an arylene group, and R1 to R3 each independently represent a hydrogen atom or an alkyl group, In formula (6), R4 represents a hydrogen atom or an alkyl group.

3. The resin composition according to claim 1, characterized in that The content of the radical compound is 0.01 to 0.4 parts by mass based on 100 parts by mass of the total of the modified polyphenylene ether compound and the curing agent.

4. The resin composition according to claim 1, characterized in that The resin composition further contains a reaction initiator.

5. The resin composition according to claim 4, characterized in that The reaction initiator comprises at least one selected from metal peroxides, azo compounds and organic peroxides.

6. The resin composition according to claim 4, characterized in that The content of the reaction initiator is 0.5 to 8.0 parts by mass based on 100 parts by mass of the total of the modified polyphenylene ether compound and the curing agent.

7. The resin composition according to claim 4, characterized in that The ratio of the free radical compound to the reaction initiator is 0.005:1.0 to 0.2:1.0 in terms of mass ratio.

8. The resin composition according to claim 1, characterized in that The resin composition further contains an inorganic filler.

9. The resin composition according to claim 1, characterized in that T1 / T2 is more than 1.0 and less than or equal to 10.0, wherein T2 represents the minimum melt viscosity and T1 represents the melt viscosity at a temperature 10° C. higher than the minimum melt viscosity.

10. The resin composition according to claim 9, characterized in that The T2 is 12,000 or less in poise, and the T1 is 15,000 or less in poise.

11. A prepreg, characterized in that include: The resin composition according to claim 1 or a semi-cured product of the resin composition; as well as Cellulosic substrate.

12. A film with resin, characterized in that include: A resin layer comprising the resin composition according to claim 1 or a semi-cured product of the resin composition; as well as Support membrane.

13. A metal foil with resin, characterized in that include: A resin layer comprising the resin composition according to claim 1 or a semi-cured product of the resin composition; as well as Metal foil.

14. A metal foil-clad laminate, characterized in that include: An insulating layer comprising a cured product of the resin composition according to claim 1 or a cured product of the prepreg according to claim 11; as well as Metal foil.

15. A wiring board, characterized in that include: An insulating layer comprising a cured product of the resin composition according to claim 1 or a cured product of the prepreg according to claim 11; as well as wiring.

16. The wiring board according to claim 15, characterized in that The wiring board includes a plurality of the insulating layers, and the wiring is arranged between the insulating layers.

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