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 containing: a polyphenylene ether compound (A) having a hydroxyl group in the molecule; a polyphenylene ether compound (B) having an unsaturated double bond in the molecule; a reactive compound (C) containing at least one compound selected from the group consisting of maleimide compounds (C1) and benzoxazine compounds (C2); and an inorganic filler (D), in which the content of the polyphenylene ether compound (A) is at least 1 part by mass and less than 50 parts by mass per 100 parts by mass of the total of the polyphenylene ether compound (A) and the polyphenylene ether compound (B).

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 rapidly. 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. In order to increase the transmission speed of signals and reduce the loss during signal transmission, the substrate material used to form the insulating layer of the wiring board used in various electronic devices is required to have a low dielectric constant and dielectric loss factor.

[0003] It is known that polyphenylene ether has excellent low dielectric properties such as low relative dielectric constant and low dielectric loss factor, and even in the high frequency band (high frequency region) from the MHz band to the GHz band, low dielectric properties such as low relative dielectric constant and low dielectric loss factor are also excellent. Therefore, the use of polyphenylene ether as, for example, a high-frequency forming material has been studied. More specifically, polyphenylene ether is preferably used as a substrate material, etc., which is used to form an insulating layer of a wiring board possessed by an electronic device utilizing a high frequency band.

[0004] Heretofore, as a resin composition containing modified polyphenylene ether, for example, Patent Document 1 discloses a polyphenylene ether resin composition containing polyphenylene ether and a cross-linking curing agent, wherein the polyphenylene ether has a polyphenylene ether portion in its molecular structure and has a p-vinylbenzyl group, a m-vinylbenzyl group, etc. at its molecular end, and has a number average molecular weight of 1000 to 7000.

[0005] The polyphenylene ether resin composition described in Patent Document 1 can provide a laminate having dielectric properties and heat resistance.

[0006] On the other hand, electronic equipment, especially small mobile devices such as mobile communication terminals and notebook computers, are rapidly developing in diversification, high performance, thinness and miniaturization. Along with this, the wiring boards used in these products also require further miniaturization of conductor wiring, multilayering, thinning of conductor wiring layers and high performance of mechanical properties. Therefore, in recent years, the requirements for various properties of the insulating layer of printed wiring boards have been further improved, requiring substrate materials with high-level desmearing properties, adhesion to metal foils, glass transition temperature and other properties while maintaining excellent dielectric (electrical) properties.

[0007] Specifically, it is desired that the insulating layer of the wiring board used in various electronic devices can properly remove the slag (smear) generated by the drilling process when drilling is performed using a drill bit, laser, etc. That is, the insulating layer of the wiring board preferably has a property that can properly remove the smear (excellent desmearing property) while suppressing damage to the insulating layer of the wiring board using permanganic acid, etc. Therefore, it is required that the substrate material used to constitute the insulating layer of the wiring board can obtain a cured product with excellent desmearing property.

[0008] Furthermore, wiring boards used in various electronic devices are also required to be less susceptible to changes in the external environment, etc. That is, in order to obtain wiring boards with excellent reliability in a wide temperature range, it is desired that the substrate material used to form the insulating layer of the wiring board can obtain a cured product with a high glass transition temperature.

[0009] In addition, the metal foil-clad laminate and the metal foil with resin used in manufacturing wiring boards and the like have not only an insulating layer but also a metal foil on the insulating layer. In addition, the wiring board also has not only an insulating layer but also wiring on the insulating layer. In addition, examples of the wiring include wiring formed of metal foil provided on the metal foil-clad laminate and the like.

[0010] It is desired that the wiring board does not peel off from the insulating layer even if the wiring is micronized. In order to meet this requirement, the wiring board preferably has high adhesion between the wiring and the insulating layer. Therefore, for the metal foil-clad laminate, it is required that the metal foil and the insulating layer have high adhesion, and for the substrate material used to constitute the insulating layer of the wiring board, it is required to be able to obtain a cured product with excellent adhesion to the metal foil.

[0011] The present invention is made in view of the above situation, and its purpose is to provide a resin composition, which can obtain a cured product with low dielectric properties, excellent desmearing properties and adhesion to metal foil and high glass transition temperature. In addition, the purpose of the present invention is to provide a prepreg, a film with resin, a metal foil with resin, a metal foil-clad laminate and a wiring board obtained by using the resin composition.

[0012] Prior art literature

[0013] Patent Literature

[0014] Patent Document 1: Japanese Patent Publication No. 2006-516297 Summary of the invention

[0015] A technical scheme of the present invention relates to a resin composition, which contains: a polyphenylene ether compound (A) having a hydroxyl group in the molecule; a polyphenylene ether compound (B) having an unsaturated double bond in the molecule; a reactive compound (C) containing at least one selected from a maleimide compound (C1) and a benzoxazine compound (C2); and an inorganic filler (D), wherein the content of the polyphenylene ether compound (A) is 1 part by mass or more and less than 50 parts by mass relative to a total of 100 parts by mass of the polyphenylene ether compound (A) and the polyphenylene ether compound (B). 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] Embodiments according to the present invention will be described below, but the present invention is not limited to these embodiments.

[0022] [Resin composition]

[0023] One embodiment of the present invention relates to a resin composition, which contains: a polyphenylene ether compound (A) having a hydroxyl group in the molecule; a polyphenylene ether compound (B) having an unsaturated double bond in the molecule; a reactive compound (C) containing at least one selected from a maleimide compound (C1) and a benzoxazine compound (C2); and an inorganic filler (D), wherein the content of the polyphenylene ether compound (A) is 1 part by mass or more and less than 50 parts by mass relative to a total of 100 parts by mass of the polyphenylene ether compound (A) and the polyphenylene ether compound (B). The resin composition of such a structure can obtain a cured product having low dielectric properties, excellent desmearing properties, and excellent adhesion to metal foil and a high glass transition temperature by curing.

[0024] According to the present embodiment, a resin composition having low dielectric properties, excellent desmearing property and adhesion to metal foil and a high glass transition temperature can be provided. In addition, according to the present embodiment, a prepreg, a film with resin, a metal foil with resin, a metal foil-clad laminate, and a wiring board obtained by using the resin composition can be provided.

[0025] (Polyphenylene ether compound (A))

[0026] The polyphenylene ether compound (A) is not particularly limited as long as it is a polyphenylene ether compound having a hydroxyl group in the molecule. The polyphenylene ether compound having a hydroxyl group in the molecule is not particularly limited as long as it is a polyphenylene ether having one or more hydroxyl groups in the molecule, and examples thereof include polyphenylene ether compounds in which hydroxyl groups remain in an unmodified state at both ends or one end of the polyphenylene ether compound. More specifically, the polyphenylene ether compound (A) has a polyphenylene ether chain in the molecule, and the polyphenylene ether compound (A) preferably has a repeating unit represented by the following formula (1) in the molecule.

[0027]

[0028] In formula (1), t represents 1 to 50. In addition, R1 to R4 are each independent. That is, R1 to R4 may be the same group or different groups. In addition, R1 to R4 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.

[0029] In R1 to R4, as each functional group listed above, specifically, the following groups can be mentioned.

[0030] 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. Specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a hexyl group, and a decyl group.

[0031] The alkenyl group is not particularly limited, and is preferably an alkenyl group having 2 to 18 carbon atoms, and more preferably an alkenyl group having 2 to 10 carbon atoms. Specifically, examples of the alkenyl group include a vinyl group, an allyl group, and a 3-butenyl group.

[0032] 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. Specifically, examples of the alkynyl group include ethynyl and prop-2-yn-1-yl (propargyl).

[0033] The alkylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted by 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. Specifically, examples of the alkylcarbonyl group include acetyl, propionyl, butyryl, isobutyryl, pivaloyl, hexanoyl, octanoyl, and cyclohexylcarbonyl.

[0034] 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. Specifically, examples of the alkenylcarbonyl group include acryloyl, methacryloyl, and crotonoyl.

[0035] The alkynylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkynyl group, and is preferably an alkynylcarbonyl group having 3 to 18 carbon atoms, and more preferably an alkynylcarbonyl group having 3 to 10 carbon atoms. Specifically, examples of the alkynylcarbonyl group include propioloyl and the like.

[0036] The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polyphenylene ether compound (A) are not particularly limited, and are preferably 500 to 5000, preferably 800 to 4000, and preferably 1000 to 3000. It is believed that by making the molecular weight 500 or more, the heat resistance of the cured product can be more reliably obtained. In addition, it is believed that by making the molecular weight 5000 or less, sufficient fluidity can be obtained, and poor molding can be suppressed. Therefore, as long as the weight average molecular weight of the polyphenylene ether compound (A) is within the above range, excellent heat resistance and moldability of the cured product can be achieved.

[0037] It should be noted that, here, the weight average molecular weight and the number average molecular weight can be any value obtained by measuring by a common molecular weight measuring method, and specifically, for example, the value measured by gel permeation chromatography (GPC) can be cited. In addition, when the polyphenylene ether compound (A) has a repeating unit represented by the formula (1) in the molecule, t is preferably a value that makes the weight average molecular weight and the number average molecular weight of the polyphenylene ether compound (A) fall within the range. Specifically, t in the formula (1) is preferably 1 to 50.

[0038] The average number of hydroxyl groups (hydroxyl number) in the polyphenylene ether compound (A) is not particularly limited, and is preferably 1 to 5, and more preferably 1.5 to 3. If the number of hydroxyl groups is too small, it tends to be difficult to obtain sufficient heat resistance of the cured product. In addition, if the number of hydroxyl groups is too large, the reactivity becomes too high, and there is a risk of, for example, reduced storage stability of the resin composition.

[0039] It should be noted that the number of hydroxyl groups of the polyphenylene ether compound (A) can be known from the specification value of the product of the polyphenylene ether compound used, for example. In addition, as the number of hydroxyl groups here, specifically, for example, the value representing the average value of the hydroxyl groups per molecule of all polyphenylene ether compounds present in 1 mol of the polyphenylene ether compound can be cited.

[0040] The intrinsic viscosity of the polyphenylene ether compound (A) is not particularly limited, and is preferably 0.03 to 0.12 dl / g, more preferably 0.04 to 0.11 dl / g, and further preferably 0.06 to 0.095 dl / g. It is believed that by making the intrinsic viscosity above 0.03 dl / g, the heat resistance of the cured product can be more reliably obtained. In addition, it is believed that by making the intrinsic viscosity below 0.12 dl / g, sufficient fluidity can be obtained, and poor molding can be suppressed. Therefore, if the intrinsic viscosity of the polyphenylene ether compound (A) is within the above range, excellent heat resistance and moldability of the cured product can be achieved.

[0041] It should be noted that the intrinsic viscosity here can be known from the specification value of the product of the polyphenylene ether compound used. In addition, the intrinsic viscosity here refers to the intrinsic viscosity measured in dichloromethane at 25°C, and more specifically, for example, the value obtained by measuring a 0.18g / 45ml dichloromethane solution (liquid temperature 25°C) with a viscometer. As such a viscometer, for example, AVS500Visco System manufactured by Schott can be cited.

[0042] The polyphenylene ether compound (A) is not particularly limited, and examples thereof include: a compound containing polyphenylene ethers including "2,6-dimethylphenol" and "at least one of a difunctional phenol and a trifunctional phenol", and poly(2,6-dimethyl-1,4-phenylene ether) as main components. More specifically, examples of the polyphenylene ether compound (A) include a polyphenylene ether compound represented by the following formula (2) and a polyphenylene ether compound represented by the following formula (3).

[0043]

[0044]

[0045] In formula (2) and formula (3), R5 to R 20 and R 21 ~R 36 are independent of each other. That is, R5~R 20 and R 21 ~R 36 They may be the same group or different groups. 20 and R 21 ~R36 , and the same groups as R1 to R4 in the above formula (1) can be mentioned. 20 and R 21 ~R 36 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. In addition, in formula (3), Y represents a linear, branched or cyclic hydrocarbon having a carbon number of 20 or less. m and n each preferably represent 0 to 20. In addition, for m and n, the total value of m and n is preferably represented by a numerical value of 1 to 30. Therefore, it is more preferred that m represents 0 to 20, n represents 0 to 20, and the total value of m and n represents 1 to 30.

[0046] In the above formula (3), 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 (4).

[0047]

[0048] In the formula (4), R 37 and R 38 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 (4) include a methylene group, a methylmethylene group, and a dimethylmethylene group, among which dimethylmethylene group is preferred.

[0049] More specific examples of the polyphenylene ether compound represented by formula (2) include, for example, the polyphenylene ether compound represented by formula (5) below. More specific examples of the polyphenylene ether compound represented by formula (3) include, for example, the polyphenylene ether compound represented by formula (6) below.

[0050]

[0051] In the above formula (5) and the above formula (6), m and n are the same as m and n in the above formula (2) and the above formula (3), and specifically, m and n are each preferably 0 to 20. In the above formula (6), Y can be the same as Y in the above formula (3).

[0052] (Polyphenylene ether (B))

[0053] The polyphenylene ether (B) is not particularly limited as long as it is a polyphenylene ether compound having an unsaturated double bond in the molecule. Examples of the polyphenylene ether compound (B) include polyphenylene ether compounds in which the polyphenylene ether compound (A) having a repeating unit represented by the above formula (1) in the molecule is terminally modified with a substituent having a carbon-carbon unsaturated double bond.

[0054] The substituent having a carbon-carbon unsaturated double bond is not particularly limited. Examples of the substituent include a substituent represented by the following formula (7).

[0055]

[0056] In formula (7), s represents 0 to 10. In addition, Z represents an arylene group. In addition, R 39 ~R 41 are independent of each other. That is, R 39 ~R 41 They may be the same group or different groups. 39 ~R 41 represents a hydrogen atom or an alkyl group.

[0057] In addition, when s in formula (7) is 0, it represents a substituent group in which Z is directly bonded to the terminal of the polyphenylene ether.

[0058] The arylene group is not particularly limited, and specifically, the arylene group includes: a monocyclic aromatic group such as a phenylene group; a polycyclic aromatic group in which the aromatic ring is not a monocyclic ring but a polycyclic aromatic group such as a naphthalene ring, etc. In addition, the arylene group also includes a derivative in which the hydrogen atom bonded to the aromatic ring is replaced by a functional group such as an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group.

[0059] 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. Specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a hexyl group, and a decyl group.

[0060] In addition, 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.

[0061] Preferred specific examples of the substituent represented by the above formula (7) include functional groups containing a vinylbenzyl group, and specifically, include at least one substituent selected from the following formula (8) or formula (9).

[0062]

[0063]

[0064] In addition, as another substituent having a carbon-carbon unsaturated double bond, a (meth)acrylate group can be mentioned, for example, represented by the following formula (10).

[0065]

[0066] In formula (10), R42 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. Specifically, examples of the alkyl group include methyl, ethyl, propyl, hexyl, and decyl groups.

[0067] The weight average molecular weight (Mw) of the polyphenylene ether compound (B) is not particularly limited, but is specifically preferably 500 to 5,000, more preferably 800 to 4,000, and even more preferably 1,000 to 3,000.

[0068] It should be noted that, here, the weight average molecular weight can be any value obtained by measuring the weight average molecular weight by a common molecular weight measuring method, and specifically, a value measured by gel permeation chromatography (GPC) can be cited. In addition, when the polyphenylene ether compound (B) has a repeating unit represented by the above formula (1) in the molecule, t is preferably a value that makes the weight average molecular weight of the modified polyphenylene ether compound fall within the above range. Specifically, t in the above formula (1) is preferably 1 to 50.

[0069] When the weight average molecular weight of the polyphenylene ether compound (B) is within the above range, the polyphenylene ether compound not only has excellent dielectric properties of polyphenylene ether, but also has excellent heat resistance and moldability of a cured product.

[0070] In addition, the average number of the substituents (terminal functional group number) of each molecule of the polyphenylene ether compound (B) at the molecular end is not particularly limited, and 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 of the resin composition or reduced fluidity of the resin composition.

[0071] It should be noted that the number of terminal functional groups of the polyphenylene ether compound (B) can be, for example, a numerical value representing the average value of the substituents present in each molecule of all polyphenylene ether compounds in 1 mol of the polyphenylene ether compound. More specifically, the number of terminal functional groups can be determined, for example, by measuring the number of hydroxyl groups remaining in the obtained polyphenylene ether compound and calculating the reduction compared to the number of hydroxyl groups of the polyphenylene ether before modification. The reduction compared to 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 polyphenylene ether compound can be obtained by adding a quaternary ammonium salt (tetraethylammonium hydroxide) associated with the hydroxyl group to a solution of the polyphenylene ether compound and measuring the UV absorbance of the mixed solution.

[0072] In addition, the intrinsic viscosity of the polyphenylene ether compound (B) is not particularly limited. Specifically, it is preferably 0.03 to 0.12 dl / g, more preferably 0.04 to 0.11 dl / g, and further preferably 0.06 to 0.095 dl / g. It is believed that by making the intrinsic viscosity above 0.03 dl / g, the heat resistance of the cured product can be more reliably obtained. In addition, it is believed that by making the intrinsic viscosity below 0.12 dl / g, sufficient fluidity can be obtained and poor molding can be suppressed. Therefore, if the intrinsic viscosity of the polyphenylene ether compound (B) is within the above range, excellent heat resistance and moldability of the cured product can be achieved.

[0073] 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.

[0074] In addition, the polyphenylene ether compound (B) may use a commercially available product or a compound produced by a known synthesis method. The synthesis method of the polyphenylene ether compound (B) is not particularly limited as long as it can synthesize a polyphenylene ether compound (B) whose terminal is modified by a substituent having a carbon-carbon unsaturated double bond. The synthesis method of the polyphenylene ether compound (B) may include, for example, a method of reacting the polyphenylene ether (A) with a compound to which a substituent having a carbon-carbon unsaturated double bond and a halogen atom are bonded.

[0075] Examples of the compound to which a substituent having a carbon-carbon unsaturated double bond and a halogen atom are bonded include compounds represented by the following formula (11).

[0076]

[0077] In formula (11), s, Z, R 39 ~R 41 and s, Z, R in the above formula (7) 39 ~R 41 Specifically, s represents 0 to 10. In addition, Z represents an arylene group. In addition, R 39 ~R 41 are independent of each other. That is, R 39 ~R 41 They may be the same group or different groups. 39 ~R 41 W represents a hydrogen atom or an alkyl group. In addition, W represents a halogen atom, and specifically, a chlorine atom, a bromine atom, an iodine atom, a fluorine atom, etc. can be mentioned. Among them, a chlorine atom is preferred.

[0078] As the compound represented by formula (11), the compounds exemplified above may be used alone or in combination of two or more.

[0079] Examples of the compound to which a substituent having a carbon-carbon unsaturated double bond and a halogen atom are bonded include p-chloromethylstyrene and m-chloromethylstyrene.

[0080] (Reactive compound (C))

[0081] The reactive compound (C) is not particularly limited as long as it is a reactive compound containing at least one selected from a maleimide compound (C1) and a benzoxazine compound (C2). In addition, as described above, the reactive compound (C) may contain only the maleimide compound (C1), may contain only the benzoxazine compound (C2), or may contain both the maleimide compound (C1) and the benzoxazine compound (C2). In addition, the reactive compound (C) preferably contains both the maleimide compound (C1) and the benzoxazine compound (C2). Accordingly, a resin composition that can obtain a cured product having excellent heat resistance and adhesion to a metal foil can be obtained more reliably.

[0082] Maleimide compound (C1)

[0083] The maleimide compound (C1) is not particularly limited as long as it is a compound having a maleimide group in the molecule. Examples of the maleimide compound (C1) 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.

[0084] Examples of the modified maleimide compound include a modified maleimide compound in which a part of the molecule is modified with an amine compound, a modified maleimide compound in which a part of the molecule is modified with an organosilicon compound, and a modified maleimide compound in which a part of the molecule is modified with an amine compound and an organosilicon compound.

[0085] In addition, the reactive compound (C) preferably contains as the maleimide compound (C1) at least one selected from the group consisting of a maleimide compound having a biphenylaralkyl structure, a maleimide compound having a phenylmaleimide group, a maleimide compound having an alkyl group having more than 6 carbon atoms, a maleimide compound having an alkylene group having more than 6 carbon atoms, and a maleimide compound having an alkyl group having more than 6 carbon atoms and an alkylene group having more than 6 carbon atoms. Thus, a resin composition capable of obtaining a cured product having an excellent relative dielectric constant and a high glass transition temperature can be obtained more reliably.

[0086] Examples of the maleimide compound having a biphenyl aralkyl structure include biphenyl aralkyl-type bismaleimide compounds, but are not limited thereto.

[0087] The maleimide compound having a phenylmaleimide group may include, for example, a maleimide compound having an arylene structure oriented and bonded at the meta position, 4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, bisphenol A diphenyl ether bismaleimide, and 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, etc. In addition, the maleimide compound having an arylene structure oriented and bonded at the meta position may include, for example, metaphenylene bismaleimide and 4-methyl-1,3-phenylene bismaleimide, etc.

[0088] Examples of the maleimide compound having an alkyl group with 6 or more carbon atoms, the maleimide compound having an alkylene group with 6 or more carbon atoms, and the maleimide compound having an alkyl group with 6 or more carbon atoms and an alkylene group with 6 or more carbon atoms include, but are not limited to, long-chain alkylbismaleimide.

[0089] In addition, the reactive compound (C) more preferably contains a maleimide compound (C1-1) comprising at least one selected from the group consisting of a maleimide compound having a biphenyl aralkyl structure and polyphenylmethane maleimide as the maleimide compound (C1). Accordingly, a resin composition having excellent adhesion to a metal foil and a cured product having a high glass transition temperature can be obtained more reliably.

[0090] The reactive compound (C) further preferably contains the maleimide compound (C1-1) and the maleimide compound (C1-2) other than the maleimide compound (C1-1) as the maleimide compound (C1). Accordingly, it is possible to more reliably obtain a resin composition that can obtain a cured product having excellent relative dielectric constant and excellent adhesion to a metal foil and a high glass transition temperature. In addition, it is believed that in the cured product of the obtained resin composition, it is possible to exert an effect of improving the uniformity of the contained components. The maleimide compound (C1-2) is preferably, for example, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, long-chain alkyl bismaleimide, etc.

[0091] The maleimide compounds (C1) described above may be used alone or in combination of two or more.

[0092] In addition, the maleimide compound (C1) can use a commercial product. Specifically, for example, BMI-1000 (4,4'-diphenylmethane bismaleimide) manufactured by Yamato Chemical Industry Co., Ltd., BMI-2300 (polyphenylmethane maleimide) manufactured by Yamato Chemical Industry Co., Ltd., BMI-3000 (meta-phenylene bismaleimide) manufactured by Yamato Chemical Industry Co., Ltd., BMI-4000 (bisphenol A diphenyl ether bismaleimide) manufactured by Yamato Chemical Industry Co., Ltd., BMI-5100 (3,3'-dimethyl-5, 5'-diethyl-4,4'-diphenylmethane bismaleimide), BMI-7000 (4-methyl-1,3-phenylene bismaleimide) manufactured by Yamato Chemical Industry Co., Ltd., MIR-3000-70T (biphenyl aralkyl type maleimide compound) manufactured by Nippon Kayaku Co., Ltd., BMI-TMH (1,6'-bismaleimide-(2,2,4-trimethyl)hexane) manufactured by Yamato Chemical Industry Co., Ltd., etc. In addition, long-chain alkyl bismaleimide can use BMI-1700, BMI-1500 and BMI-689 manufactured by Designer Molercules Inc.

[0093] Benzoxazine compounds (C2)

[0094] The benzoxazine compound (C2) is a compound having a benzoxazine ring in the molecule, and benzoxazine resins and the like can be cited. As the benzoxazine compound (C2), for example, a benzoxazine compound having a phenolphthalein structure in the molecule (phenolphthalein type benzoxazine compound), a benzoxazine compound having an alkenyl group in the molecule, a bisphenol F type benzoxazine compound, and a diaminodiphenylmethane (DDM) type benzoxazine compound can be cited. As the benzoxazine compound (C2), more specifically, 3,3'-(methylene-1,4-diphenylene)bis(3,4-dihydro-2H-1,3-benzoxazine) (Pd type benzoxazine compound) and 2,2-bis(3,4-dihydro-2H-3-phenyl-1,3-benzoxazine)methane (Fa type benzoxazine compound) can be cited. The benzoxazine compound (C2) can be used alone or in combination of two or more.

[0095] Among the benzoxazine compounds (C2), a benzoxazine compound (C2-1) having an alkenyl group in the molecule is preferably used. By using a benzoxazine compound (C2-1) having an alkenyl group, a resin composition that can obtain a cured product having better adhesion to a metal foil and a higher glass transition temperature can be obtained more reliably.

[0096] The alkenyl group is not particularly limited, and examples thereof include alkenyl groups having 2 to 6 carbon atoms. Specific examples of the alkenyl group include vinyl groups, allyl groups, and butenyl groups, and among these, allyl groups are preferred.

[0097] In addition, as the benzoxazine compound (C2-1) having an alkenyl group, for example, a compound having a benzoxazine group in the molecule and the benzoxazine group having an alkenyl group, etc. can be cited. As the benzoxazine group (benzoxazine group having an alkenyl group), for example, a benzoxazine group represented by the following formula (12) and a benzoxazine group represented by the following formula (13) can be cited. As the benzoxazine compound having an alkenyl group in the molecule, for example, a benzoxazine compound having a benzoxazine group represented by the following formula (12) in the molecule, a benzoxazine compound having a benzoxazine group represented by the following formula (13) in the molecule, and a benzoxazine compound having a benzoxazine group represented by the following formula (12) and a benzoxazine group represented by the following formula (13) in the molecule can be cited. As the benzoxazine compound having a benzoxazine group represented by the following formula (12) in the molecule, for example, a benzoxazine compound represented by the following formula (14) can be cited.

[0098]

[0099] In formula (12), R 43 represents alkenyl, p is R 43The average value of the degree of substitution is 1 to 4, preferably 1.

[0100]

[0101] In formula (13), R 44 It represents an alkenyl group.

[0102]

[0103] In formula (14), R 45 and R 46 Each independently represents an alkenyl group, X represents an alkylene group, and q and r each independently represent 1 to 4.

[0104] The alkenyl group in the formulae (12) to (14) is not particularly limited as described above, but is preferably an allyl group.

[0105] The alkylene group is not particularly limited, and examples thereof include methylene, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octyl, eicosyl, hexatriacontyl, etc. Among them, the alkylene group is preferably methylene.

[0106] In the formula (14), q is R 45 The average substitution degree is 1 to 4, preferably 1. In addition, r in the formula (14) is R 46 The average value of the degree of substitution is 1 to 4, preferably 1.

[0107] The benzoxazine compound (C2) may be a commercial product. For example, the benzoxazine compound having an alkenyl group may be an ALP-d type benzoxazine compound manufactured by Shikoku Chemicals Co., Ltd., etc. In addition, the 3,3'-(methylene-1,4-diphenylene)bis(3,4-dihydro-2H-1,3-benzoxazine) may be a Pd type benzoxazine compound manufactured by Shikoku Chemicals Co., Ltd., etc.

[0108] Other reactive compounds

[0109] In addition, the reactive compound (C) may contain other reactive compounds (C3) in addition to at least one selected from the maleimide compound (C1) and the benzoxazine compound (C2). Examples of the other reactive compound (C3) include allyl compounds, acrylate compounds, methacrylate compounds, polybutadiene compounds, vinyl compounds such as styrene compounds, acenaphthylene compounds, cyanate compounds, epoxy compounds, and active ester compounds.

[0110] The allyl compound is a compound having an allyl group in the molecule, and examples thereof include triallyl isocyanurate compounds such as triallyl isocyanurate (TAIC), diallyl bisphenol compounds, and diallyl phthalate (DAP).

[0111] The acrylate compound is a compound having an acryloyl group in the molecule, and examples thereof 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 diacrylate compounds such as tricyclodecane dimethanol diacrylate.

[0112] The methacrylate compound is a compound having a methacryloyl group in the molecule, and examples thereof 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 dimethacrylate compounds such as tricyclodecane dimethanol dimethacrylate (DCP), and the like.

[0113] The vinyl compound is a compound having a vinyl group in the molecule. Examples of the vinyl compound include monofunctional vinyl compounds (monovinyl compounds) having one vinyl group in the molecule and polyfunctional vinyl compounds having two or more vinyl groups in the molecule. Examples of the monofunctional vinyl compound include styrene compounds. Examples of the polyfunctional vinyl compound include polyfunctional aromatic vinyl compounds and vinyl hydrocarbon compounds. In addition, examples of the vinyl hydrocarbon compound include divinylbenzene and polybutadiene compounds.

[0114] The acenaphthylene compound is a compound having an acenaphthylene structure in the molecule. 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.

[0115] The cyanate compound is a compound having a cyano group in the molecule, and examples thereof include 2,2-bis(4-cyanatophenyl)propane, bis(3,5-dimethyl-4-cyanatophenyl)methane, and 2,2-bis(4-cyanatophenyl)ethane.

[0116] The epoxy compound is a compound having an epoxy group in the molecule, and examples thereof include epoxy compounds having a naphthalene skeleton and epoxy compounds having a dicyclopentadiene skeleton.

[0117] The active ester compound is a compound having an ester group with high reactivity in the molecule, and examples thereof include benzenecarboxylic acid active ester, benzenedicarboxylic acid active ester, benzenetricarboxylic acid active ester, benzenetetracarboxylic acid active ester, naphthalenecarboxylic acid active ester, naphthalenedicarboxylic acid active ester, naphthalenetricarboxylic acid active ester, naphthalenetetracarboxylic acid active ester, fluorenecarboxylic acid active ester, fluorenedicarboxylic acid active ester, fluorenetricarboxylic acid active ester, and fluorenetetracarboxylic acid active ester. ester) etc.

[0118] When the reactive compound (C) contains the other reactive compound (C3) other than the maleimide compound (C1) and the benzoxazine compound (C2), the reactive compound (C3) described above may be used alone or in combination of two or more.

[0119] (Inorganic filler (D))

[0120] The inorganic filler (D) is not particularly limited as long as it can be used as an inorganic filler contained in the resin composition. As the inorganic filler (D), for example, metal oxides such as silicon dioxide, aluminum oxide, titanium oxide, magnesium oxide and mica, metal hydroxides such as magnesium hydroxide and aluminum hydroxide, talc, aluminum borate, barium sulfate, aluminum nitride, boron nitride, barium titanate, magnesium carbonate such as anhydrous magnesium carbonate, and calcium carbonate, etc. can be cited. Among them, metal hydroxides such as silicon dioxide, magnesium hydroxide and aluminum hydroxide, aluminum oxide, boron nitride, and barium titanate, etc. are preferred, and silicon dioxide is more preferred. The silicon dioxide is not particularly limited, and for example, crushed silicon dioxide, spherical silicon dioxide, and silicon dioxide particles can be cited.

[0121] The inorganic filler (D) may be a surface-treated inorganic filler or an untreated inorganic filler. Examples of the surface treatment include treatment with a silane coupling agent.

[0122] Examples of the silane coupling agent include a silane coupling agent having at least one functional group selected from the group consisting of a vinyl group, a styryl group, a methacryl group, an acryl group, an aniline group, an isocyanurate group, a urea group, a mercapto group, an isocyanate group, an epoxy group, and an acid anhydride group. That is, examples of the silane coupling agent include a compound having at least one of a vinyl group, a styryl group, a methacryl group, an acryl group, an aniline group, an isocyanurate group, a urea group, a mercapto group, an isocyanate group, an epoxy group, and an acid anhydride group as a reactive functional group and having a hydrolyzable group such as a methoxy group or an ethoxy group.

[0123] Regarding the silane coupling agent, as a silane coupling agent having a vinyl group, for example, vinyl triethoxysilane and vinyl trimethoxysilane can be cited. Regarding the silane coupling agent, as a silane coupling agent having a styrene group, for example, p-styrene trimethoxysilane and p-styrene triethoxysilane can be cited. Regarding the silane coupling agent, as a silane coupling agent having a methacryloyl group, for example, 3-methacryloyloxypropyl trimethoxysilane, 3-methacryloyloxypropyl methyl dimethoxysilane, 3-methacryloyloxypropyl triethoxysilane, 3-methacryloyloxypropyl methyl ethoxysilane, and 3-methacryloyloxypropyl ethyl diethoxysilane can be cited. Regarding the silane coupling agent, as a silane coupling agent having an acryl group, for example, 3-acryloyloxypropyl trimethoxysilane and 3-acryloyloxypropyl triethoxysilane can be cited. As for the silane coupling agent, examples of the silane coupling agent having a phenylamino group include N-phenyl-3-aminopropyltrimethoxysilane and N-phenyl-3-aminopropyltriethoxysilane.

[0124] The average particle size of the inorganic filler (D) is not particularly limited, and is preferably 0.05 to 10 μm, and more preferably 0.1 to 8 μm. It should be noted that the average particle size here refers to the volume average particle size, which can be measured by, for example, laser diffraction method.

[0125] (content)

[0126] The content of the polyphenylene ether compound (A) is 1 part by mass or more and less than 50 parts by mass relative to a total of 100 parts by mass of the polyphenylene ether compound (A) and the polyphenylene ether compound (B). By making the polyphenylene ether compound (A) 1 part by mass or more, there is an advantage that a resin composition capable of obtaining a cured product having excellent desmearing properties can be provided. In addition, by making the polyphenylene ether compound (A) less than 50 parts by mass, there is an advantage that a resin composition capable of obtaining a cured product having excellent adhesion to a metal foil and desmearing properties can be provided.

[0127] The content of the polyphenylene ether compound (A) is preferably 3 to 45 parts by mass based on 100 parts by mass of the total of the polyphenylene ether compound (A) and the polyphenylene ether compound (B).

[0128] In addition, the content of the polyphenylene ether compound (A) is preferably 0.1 to 45 parts by mass relative to a total of 100 parts by mass of the polyphenylene ether compound (A), the polyphenylene ether compound (B) and the reactive compound (C). By making the polyphenylene ether compound (A) 0.1 parts by mass or more, a resin composition capable of obtaining a cured product having excellent desmearing properties can be obtained more reliably. In addition, by making the polyphenylene ether compound (A) 45 parts by mass or less, a resin composition capable of obtaining a cured product having excellent adhesion to a metal foil and desmearing properties can be obtained more reliably.

[0129] The lower limit of the content of the polyphenylene ether compound (A) is more preferably 3 parts by mass or more, and further preferably 5 parts by mass or more, relative to 100 parts by mass of the total of the polyphenylene ether compound (A), the polyphenylene ether compound (B) and the reactive compound (C). In addition, the upper limit of the content of the polyphenylene ether compound (A) is preferably 40 parts by mass or less, and more preferably 30 parts by mass or less.

[0130] In addition, relative to the total of 100 parts by mass of the polyphenylene ether compound (A), the polyphenylene ether compound (B) and the reactive compound (C), the content of the polyphenylene ether compound (B) is preferably 10 to 70 parts by mass. By making the polyphenylene ether compound (B) 10 parts by mass or more, it is possible to more reliably obtain a resin composition that can obtain a cured product having excellent adhesion to a metal foil and a relative dielectric constant. By making the polyphenylene ether compound (B) 70 parts by mass or less, it is possible to more reliably obtain a resin composition that can obtain a cured product having excellent desmearing properties.

[0131] The lower limit of the content of the polyphenylene ether compound (B) is more preferably 15 parts by mass or more, and more preferably 20 parts by mass or more, relative to 100 parts by mass of the total of the polyphenylene ether compound (A), the polyphenylene ether compound (B) and the reactive compound (C). In addition, the upper limit of the content of the polyphenylene ether compound (B) is more preferably 65 parts by mass or less, and more preferably 60 parts by mass or less.

[0132] In addition, the content of the reactive compound (C) is not particularly limited, and is preferably 10 to 80 parts by mass relative to a total of 100 parts by mass of the polyphenylene ether compound (A), the polyphenylene ether compound (B) and the reactive compound (C). By making the content of the reactive compound (C) 10 parts by mass or more, a resin composition capable of obtaining a cured product with a high glass transition temperature can be more reliably obtained. By making the content of the reactive compound (C) 80 parts by mass or less, a resin composition capable of obtaining a cured product with excellent relative dielectric constant can be more reliably obtained.

[0133] The lower limit of the content of the reactive compound (C) is more preferably 15 parts by mass or more, and more preferably 20 parts by mass or more, relative to 100 parts by mass of the total of the polyphenylene ether compound (A), the polyphenylene ether compound (B) and the reactive compound (C). In addition, the upper limit of the content of the reactive compound (C) is more preferably 75 parts by mass or less, and more preferably 70 parts by mass or less.

[0134] When the reactive compound (C) contains the maleimide compound (C1), the content of the maleimide compound (C1) is preferably 10 to 70 parts by mass relative to 100 parts by mass of the total of the polyphenylene ether compound (A), the polyphenylene ether compound (B) and the reactive compound (C). By setting the above range, there is an advantage that a resin composition that can obtain a cured product having an excellent relative dielectric constant and a high glass transition temperature can be obtained more reliably.

[0135] The lower limit of the content of the maleimide compound (C1) is more preferably 15 parts by mass or more, and more preferably 20 parts by mass or more, relative to 100 parts by mass of the total of the polyphenylene ether compound (A), the polyphenylene ether compound (B) and the reactive compound (C). In addition, the upper limit of the content of the maleimide compound (C1) is more preferably 65 parts by mass or less, and more preferably 60 parts by mass or less.

[0136] When the reactive compound (C) contains the benzoxazine compound (C2), the content of the benzoxazine compound (C2) is preferably 1 to 70 parts by mass or more relative to 100 parts by mass of the total of the polyphenylene ether compound (A), the polyphenylene ether compound (B) and the reactive compound (C). By setting the content within the above range, there is an advantage that a resin composition capable of obtaining a cured product having a higher glass transition temperature can be obtained.

[0137] The lower limit of the content of the benzoxazine compound (C2) is more preferably 3 parts by mass or more, and further preferably 5 parts by mass or more, based on 100 parts by mass of the total of the polyphenylene ether compound (A), the polyphenylene ether compound (B), and the reactive compound (C).

[0138] As the upper limit of the content of the benzoxazine compound (C2), when the reactive compound (C) does not contain the maleimide compound (C1) but contains the benzoxazine compound (C2), the content of the benzoxazine compound (C2) is more preferably 60 parts by mass or less, and further preferably 50 parts by mass or less, relative to 100 parts by mass of the total of the polyphenylene ether compound (A), the polyphenylene ether compound (B) and the reactive compound (C). In addition, when the reactive compound (C) contains both the maleimide compound (C1) and the benzoxazine compound (C2), the content of the benzoxazine compound (C2) is more preferably 50 parts by mass or less, further preferably 40 parts by mass or less, and most preferably 20 parts by mass or less, relative to 100 parts by mass of the total of the polyphenylene ether compound (A), the polyphenylene ether compound (B) and the reactive compound (C).

[0139] Furthermore, when the reactive compound (C) contains a maleimide compound (C1-1) selected from the group consisting of a maleimide compound having a biphenyl aralkyl structure and a polyphenylmethane maleimide, and a maleimide compound (C1-2) other than the maleimide compound (C1-1), the content of the maleimide compound (C1-1) is preferably 10 to 90 parts by mass, more preferably 10 to 80 parts by mass, and even more preferably 25 to 60 parts by mass, relative to 100 parts by mass of the maleimide compound (C1) (relative to 100 parts by mass of the total of the maleimide compound (C1-1) and the maleimide compound (C1-2)). By making the content of the maleimide compound (C1-1) 10 to 90 parts by mass relative to a total of 100 parts by mass of the maleimide compound (C1), it is possible to more reliably obtain a resin composition that can obtain a cured product having excellent relative dielectric constant and adhesion to a metal foil and a high glass transition temperature. In addition, it is believed that in the cured product of the obtained resin composition, the uniformity of the contained components can be improved.

[0140] Furthermore, when the reactive compound (C) contains the other reactive compound (C3) in addition to at least one selected from the maleimide compound (C1) and the benzoxazine compound (C2), the content of the other reactive compound (C3) is preferably 1 to 40 parts by mass, and more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the reactive compound (C).

[0141] The content of the inorganic filler (D) is not particularly limited, and is preferably 10 to 250 parts by mass relative to a total of 100 parts by mass of the polyphenylene ether compound (A), the polyphenylene ether compound (B) and the reactive compound (C). By making the content of the inorganic filler (D) 10 parts by mass or more, there is an advantage that a resin composition that can obtain a cured product with better dimensional stability can be obtained. By making the content of the inorganic filler 250 parts by mass or less, there is an advantage that a resin composition that can obtain a cured product with better moldability can be obtained.

[0142] The lower limit of the content of the inorganic filler (D) is more preferably 40 parts by mass or more, and more preferably 60 parts by mass or more, relative to 100 parts by mass of the total of the polyphenylene ether compound (A), the polyphenylene ether compound (B) and the reactive compound (C). In addition, the upper limit of the content of the inorganic filler (D) is more preferably 200 parts by mass or less, and more preferably 180 parts by mass or less.

[0143] (Other ingredients)

[0144] The resin composition involved in the present embodiment may contain components (other components) other than the polyphenylene ether compound (A), the polyphenylene ether compound (B), the reactive compound (C) and the inorganic filler (D) as required within the scope of not impairing the effect of the present invention. As other components contained in the resin composition involved in the present embodiment, not only the inorganic filler as described above is contained, but also additives such as reaction initiators, curing accelerators, catalysts, polymerization retarders, polymerization inhibitors, dispersants, leveling agents, silane coupling agents, defoamers, antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, dyes or pigments, and lubricants may also be contained.

[0145] As described above, the resin composition involved in the present embodiment may contain a reaction initiator. Even if the resin composition does not contain a reaction initiator, a curing reaction can be carried out. However, depending on the process conditions, it is sometimes difficult to raise the temperature until the curing is carried out, so a reaction initiator may also be added. The reaction initiator is not particularly limited as long as it can promote the curing reaction of the resin composition, and examples thereof include peroxides and organic azo compounds. As the peroxide, examples thereof include diisopropyl peroxide, α, α'-bis(tert-butylperoxym-isopropyl)benzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne, and benzoyl peroxide. In addition, as the organic azo compound, examples thereof include azobisisobutyronitrile, etc. In addition, carboxylic acid metal salts, etc., may be used in combination as needed. Accordingly, the curing reaction may be further promoted. Among them, α, α'-bis(tert-butylperoxym-isopropyl)benzene is preferably used. α, α'-bis(tert-butylperoxy-m-isopropyl)benzene has a relatively high reaction starting temperature, so it can inhibit the promotion of the curing reaction when the prepreg is dried and does not need to be cured, and can inhibit the reduction of the storage property of the resin composition. In addition, α, α'-bis(tert-butylperoxy-m-isopropyl)benzene has low volatility, so it will not volatilize when the prepreg is dried and stored, and has good stability. In addition, the reaction initiator can be used alone or in combination of two or more.

[0146] As described above, the resin composition involved in the present embodiment may contain a curing accelerator. The curing accelerator is not particularly limited as long as it can promote the curing reaction of the resin composition. As the curing accelerator, specifically, amines such as imidazoles and their derivatives, organic phosphine compounds, secondary amines and tertiary amines, quaternary ammonium salts, organic boron compounds, and metal soaps can be cited. As the imidazoles, for example, 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-phenyl-4-methylimidazole, 2-phenylimidazole, and 1-benzyl-2-methylimidazole can be cited. In addition, as the organic phosphine compounds, triphenylphosphine, diphenylphosphine, phenylphosphine, tributylphosphine and trimethylphosphine can be cited. In addition, as the amines, for example, dimethylbenzylamine, triethylenediamine, triethanolamine, 1,8-diazabicyclo (5,4,0) undecene-7 (DBU) can be cited. In addition, as the quaternary ammonium salts, tetrabutylammonium bromide can be cited. In addition, examples of the organic boron compound include tetraphenyl borate salts such as 2-ethyl-4-methylimidazoletetraphenylborate, and tetraphenylphosphonium ethyltriphenylborate, and tetrasubstituted phosphonium tetrasubstituted borate. In addition, the metal soap refers to a fatty acid metal salt, which may be a linear fatty acid metal salt or a cyclic fatty acid metal salt. Specifically, examples of the metal soap include linear aliphatic metal salts and cyclic aliphatic metal salts having 6 to 10 carbon atoms. More specifically, examples include aliphatic metal salts formed by linear fatty acids such as stearic acid, lauric acid, ricinoleic acid, and octanoic acid, or cyclic fatty acids such as cyclopentane acid, and metals such as lithium, magnesium, calcium, barium, copper, and zinc. For example, zinc octanoate may be cited. The curing accelerators may be used alone or in combination of two or more.

[0147] As described above, the resin composition involved in the present embodiment may contain a silane coupling agent. As far as the silane coupling agent is concerned, the silane coupling agent may be directly contained in the resin composition, or may be contained as a silane coupling agent used when the inorganic filler is subjected to a pre-surface treatment. Wherein, as the silane coupling agent, it is preferably contained as a silane coupling agent used when the inorganic filler is subjected to a pre-surface treatment. In addition, it is more preferred that the silane coupling agent is contained as a silane coupling agent used when the inorganic filler is subjected to a pre-surface treatment, and the silane coupling agent is directly contained in the resin composition. In addition, as far as the prepreg is concerned, the silane coupling agent used when the fibrous substrate is subjected to a pre-surface treatment may be contained in the prepreg. As the silane coupling agent, for example, the silane coupling agent identical to the silane coupling agent used when the inorganic filler is subjected to a surface treatment as described above may be cited.

[0148] 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 flame retardants such as brominated flame retardants, bromostyrene compounds are preferred, such as: ethylenedipentabromobenzene, ethylenebistetrabromoimide, decabromodiphenyl ether, tetradecabromodiphenoxybenzene having a melting point of more than 300°C; and bromostyrene compounds reacting with the polymerizable compound. It is believed that by using a halogen flame retardant, the detachment of halogen at high temperature can be suppressed, and the reduction of heat resistance can be suppressed. In addition, in the field requiring halogen-free, phosphorus-containing flame retardants (phosphorus flame retardants) are sometimes used. The phosphorus-based flame retardant is not particularly limited, and examples thereof include: phosphate ester-based flame retardant, phosphazene-based flame retardant, bisdiphenylphosphine-based flame retardant, and phosphinate-based flame retardant. As a specific example of the phosphate ester flame retardant, a condensed phosphate ester of dixylyl phosphate can be cited. As a specific example of the phosphazene flame retardant, phenoxyphosphazene can be cited. As a specific example of the bisdiphenylphosphine flame retardant, xylene bis(diphenylphosphine oxide) can be cited. As a specific example of the hypophosphite flame retardant, for example, a hypophosphite metal salt of a dialkyl hypophosphite aluminum salt can be cited. As the flame retardant, one of the exemplified flame retardants can be used alone, or two or more can be used in combination.

[0149] (use)

[0150] As described later, the resin composition is used when manufacturing prepreg. In addition, the resin composition is used when forming a resin layer provided on a metal foil with resin and a film with resin, and an insulating layer provided on a metal foil-clad laminate and a wiring board. In addition, the resin composition can obtain a cured product with excellent low dielectric properties such as low relative dielectric constant as described above. Therefore, the resin composition is suitable for forming an insulating layer provided in a wiring board for high frequency such as a wiring board for antenna, an antenna substrate for millimeter-wave radar, etc. That is, the resin composition is suitable for manufacturing a wiring board for high frequency.

[0151] (Manufacturing method)

[0152] The method for producing the resin composition is not particularly limited, and examples thereof include a method of mixing the polyphenylene ether compound (A), the polyphenylene ether compound (B), the reactive compound (C) and the inorganic filler (D) under conditions of a specified content, etc. In addition, in the case of obtaining a varnish-like composition containing an organic solvent, the method described below, etc., can be cited.

[0153] Next, the prepreg, metal foil-clad laminate, wiring board, metal foil with resin, and film with resin using the resin composition involved in the present embodiment are described with reference to the accompanying drawings. It should be noted that in each of the drawings, 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 plate with resin; 32, 42: resin layer; 41: film with resin; 43: supporting film.

[0154] [Prepreg]

[0155] Figure 1 This is a schematic cross-sectional view showing an example of the prepreg 1 according to the embodiment of the present invention.

[0156] 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.

[0157] It should be noted that, in the present embodiment, semi-cured material is a material that cures the resin combination to a state that can further be cured midway. That is, semi-cured material is a material that makes the state (B-stage) of the resin combination semi-cured. For example, if the resin combination is heated, the initial viscosity is slowly reduced, and then begins to solidify, and the viscosity slowly rises. In this case, as semi-cured, the state during the period from when the viscosity begins to rise to before fully solidified, etc. can be cited.

[0158] As the prepreg obtained by using the resin composition involved in the present embodiment, it can be a prepreg with a semi-cured product of the resin composition as described above, and it can also be a prepreg with an uncured resin composition. That is, it can be a prepreg with 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 with 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.

[0159] When manufacturing the prepreg, the resin composition 2 is often used in a varnish state in order to be impregnated into the substrate for forming the prepreg, i.e., the fibrous substrate 3. That is, the resin composition 2 is usually often a resin varnish prepared in a varnish state. The varnish-like resin composition (resin varnish) can be prepared, for example, in the following manner.

[0160] First, each component soluble in an organic solvent is put into an organic solvent and dissolved. At this time, heating can be performed as needed. Then, a component insoluble in an organic solvent used as needed is added, and a ball mill, a bead mill, a planetary mixer, a roller mill, etc. are used to disperse it to a specified dispersed state, thereby a varnish-like resin composition can be modulated. As the organic solvent used herein, as long as it is an organic solvent that can dissolve the polyphenylene ether compound (A), the polyphenylene ether compound (B) and the reactive compound (C) and the like and does not hinder the curing reaction, it is not particularly limited. Specifically, for example, toluene, methyl ethyl ketone (MEK) etc. can be cited.

[0161] 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 the 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. In addition, the glass fiber constituting the glass cloth is not particularly limited, and for example, Q glass, NE glass, E glass, S glass, T glass, L glass and L2 glass can be cited. In addition, the surface of the fibrous substrate can be surface treated with a silane coupling agent. The silane coupling agent is not particularly limited, and examples thereof include silane coupling agents having at least one group selected from the group consisting of a vinyl group, an acryloyl group, a methacryloyl group, a styryl group, an amino group, and an epoxy group in the molecule.

[0162] 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.

[0163] As a method for manufacturing the prepreg 1, specifically, there can be cited a method of impregnating the resin composition 2 (for example, a resin composition 2 modulated into a varnish state) into a fibrous substrate 3 and then drying it. The impregnation of the resin composition 2 into the fibrous substrate 3 is performed by impregnation and coating, etc. The impregnation can also be repeated multiple times as needed. Moreover, at this time, it is also possible to adjust the final desired composition and impregnation amount by repeatedly impregnating with multiple resin compositions with different compositions and concentrations.

[0164] The fibrous substrate 3 impregnated with the resin composition (resin varnish) 2 is heated under the required heating conditions (for example, heating at 40° 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.

[0165] The resin combination that the present embodiment is related to is the resin combination that can obtain the solidified product with low dielectric properties, desmear property and excellent adhesion with metal foil and high glass transition temperature.Therefore, the prepreg of the semi-cured product possessing this resin combination or this resin combination is the prepreg that can obtain the solidified product with low dielectric properties, desmear property and excellent adhesion with metal foil and high glass transition temperature.And, this prepreg can well manufacture the wiring board of the insulating layer of the solidified product possessing low dielectric properties, desmear property and excellent adhesion with metal foil and high glass transition temperature.

[0166] [Metal foil laminate]

[0167] 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.

[0168] like Figure 2 As shown, the metal-clad laminate 11 according to the present embodiment includes: an insulating layer 12 including a cured product of the resin composition; and a metal foil 13 provided on the insulating layer 12. Examples of the metal-clad laminate 11 include a laminate including Figure 1 An insulating layer 12 of a cured product of the prepreg 1 shown; and a metal foil-clad laminate of a metal foil 13 stacked on both upper and lower side surfaces or a single side surface of the insulating layer 12. In addition, the insulating layer 12 can be formed by a cured product of the resin composition, or by a cured product of the prepreg. In addition, the thickness of the metal foil 13 varies depending on the performance required of the final wiring board, and is not particularly limited. The thickness of the metal foil 13 can be appropriately set according to the desired 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 operability, it can be a copper foil with a carrier having a peeling layer and a carrier.

[0169] 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 manufacturing the metal foil-clad laminate 11 using the prepreg 1 can be cited. As this method, a method can be cited as follows: taking a piece of the prepreg 1 or overlapping several pieces of the prepreg 1, and then overlapping a metal foil 13 such as copper foil on the upper and lower surfaces or one side surface thereof, and heating and pressing the metal foil 13 and the prepreg 1 to form a laminate 11 with metal foil on both sides or one side, etc. can be made. That is, the metal foil-clad laminate 11 is obtained by stacking the metal foil 13 on the prepreg 1 and heating and pressing it. In addition, the conditions for heating and pressing can be appropriately set according to the thickness of the metal foil-clad laminate 11 or the type of resin composition contained in the prepreg 1. For example, the temperature can be set to 170 to 230°C, the pressure can be set to 2 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.

[0170] The resin composition involved in the present embodiment is a resin composition that can obtain a cured product having low dielectric properties, excellent desmear properties, and excellent adhesion to metal foil, and a high glass transition temperature. Therefore, a metal-clad laminate having an insulating layer of a cured product comprising the resin composition is a metal-clad laminate having an insulating layer of a cured product having low dielectric properties, excellent desmear properties, and excellent adhesion to metal foil, and a high glass transition temperature.

[0171] In addition, the prepreg involved in the present embodiment is a prepreg that can obtain a cured product having low dielectric properties, excellent desmear properties and adhesion to metal foil, and a high glass transition temperature. Therefore, the metal-clad laminate having an insulating layer of a cured product including the prepreg is a metal-clad laminate having an insulating layer including a cured product having low dielectric properties, excellent desmear properties and adhesion to metal foil, and a high glass transition temperature.

[0172] Furthermore, the metal foil-clad laminate can satisfactorily produce a wiring board having an insulating layer including a cured product having low dielectric properties, excellent desmear properties and adhesion to metal foil and a high glass transition temperature.

[0173] [Wiring board]

[0174] Figure 3 It is a schematic cross-sectional view showing an example of wiring board 21 according to the embodiment of the present invention.

[0175] like Figure 3As shown, the wiring board 21 according to the present embodiment includes: an insulating layer 12 including a cured product of the resin composition; and wiring 14 provided on both upper and lower surfaces or one side of the insulating layer 12. Examples of the wiring board 21 include: Figure 1 The insulating layer 12 is used by curing the prepreg 1; and a wiring board with wiring 14 formed by removing a part of the metal foil 13 and stacking on both sides or one side of the upper and lower surfaces of the insulating layer 12. In addition, the insulating layer 12 can be formed by the cured product of the resin composition or the cured product of the prepreg.

[0176] 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 the 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-clad laminate 11 manufactured as described above, and the like can be cited. That is, the wiring board 21 can be obtained by removing a portion of the metal foil 13 on the surface of the metal foil-clad laminate 11, thereby forming 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, for example, a semi-additive process (SAP: SemiAdditive Process) or a modified semi-additive process (MSAP: Modified SemiAdditive Process) can be cited.

[0177] The wiring board 21 is a wiring board including the insulating layer 12 including a cured product having low dielectric properties, excellent desmear properties and adhesion to metal foil and a high glass transition temperature.

[0178] [Metal foil with resin]

[0179] Figure 4 1 is a schematic cross-sectional view showing an example of a metal foil 31 with resin according to an embodiment of the present invention.

[0180] 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.

[0181] 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 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.

[0182] As the metal foil, metal foils used in metal foil-clad laminates and metal foils with resins can be used without limitation. Examples of the metal foil include copper foil and aluminum foil.

[0183] The metal foil with resin 31 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.

[0184] 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 coater. The applied resin composition is heated under conditions of, for example, 40°C to 180°C and 0.1 minutes 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.

[0185] The resin composition that the present embodiment is related to is a resin composition that can obtain a cured product with low dielectric properties, desmearing property, and excellent adhesion to metal foil and a high glass transition temperature. Therefore, the metal foil with resin having a resin layer of a semi-cured product comprising the resin composition or the resin composition is a metal foil with resin having a resin layer of a cured product with low dielectric properties, desmearing property, and excellent adhesion to metal foil and a high glass transition temperature. And, the metal foil with resin can be used when manufacturing a wiring board with an insulating layer of a cured product comprising low dielectric properties, desmearing property, and excellent adhesion to metal foil and a high glass transition temperature. For example, a multilayer wiring board can be manufactured by being stacked on a wiring board. As the wiring board obtained by using the metal foil with resin, a wiring board with an insulating layer of a cured product comprising low dielectric properties, desmearing property, and excellent adhesion to metal foil and a high glass transition temperature can be obtained.

[0186] [Film with resin]

[0187] Figure 5 It is a schematic cross-sectional view showing an example of the film 41 with resin according to the embodiment of the present invention.

[0188] 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.

[0189] 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.

[0190] As the supporting film 43, any supporting film used in a film with a resin can be used without limitation. 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.

[0191] The film 41 with resin may include a cover film etc. as needed. By including the cover film, it is possible to prevent foreign matter from being mixed in. The cover film is not particularly limited, and examples thereof include polyolefin films, polyester films, and polymethylpentene films.

[0192] 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.

[0193] The method for manufacturing the resin-bearing film 41 is not particularly limited as long as the resin-bearing film 41 can be manufactured. The method for manufacturing the resin-bearing film 41 may include, for example, a method of applying the above-mentioned varnish-like resin composition (resin varnish) on the supporting film 43 and heating it. For example, the varnish-like resin composition is applied to the supporting film 43 using a scraper coater. The applied resin composition is heated under conditions of, for example, 40°C to 180°C and 0.1 minutes to 10 minutes. The heated resin composition is formed on the supporting film 43 as an uncured resin layer 42. It should be noted that by volatilizing the organic solvent from the resin varnish through the heating, the organic solvent can be reduced or removed.

[0194] The resin composition that the present embodiment is related to is a resin composition that can obtain a cured product with low dielectric properties, desmearing property, and excellent adhesion to metal foil and a high glass transition temperature. Therefore, the film with resin of the resin layer of the semi-cured product comprising the resin composition or the resin composition is a film with resin of the resin layer of the cured product with low dielectric properties, desmearing property, and excellent adhesion to metal foil and a high glass transition temperature. And, the film with resin can be used when the wiring board with the insulating layer of the cured product with low dielectric properties, desmearing property, and excellent adhesion to metal foil and a high glass transition temperature is manufactured. For example, it is possible to peel off the supporting film after being stacked on the wiring board, or, after peeling off the supporting film, stacked on the wiring board, to manufacture a multilayer wiring board. As the wiring board obtained using the film with resin, it is possible to obtain a wiring board with an insulating layer of a cured product with low dielectric properties, desmearing property, and excellent adhesion to metal foil and a high glass transition temperature.

[0195] As described above, according to the present invention, a resin composition having low dielectric properties, excellent desmearing properties and adhesion to metal foil and a high glass transition temperature can be provided. In addition, according to the present invention, a prepreg, a film with resin, a metal foil with resin, a metal foil-clad laminate, and a wiring board obtained by using the resin composition can be provided.

[0196] As described above, this specification discloses various types of technologies, and the main technologies are summarized as follows.

[0197] The resin composition of the first technical solution contains: a polyphenylene ether compound (A) having a hydroxyl group in the molecule; a polyphenylene ether compound (B) having an unsaturated double bond in the molecule; a reactive compound (C) containing at least one selected from a maleimide compound (C1) and a benzoxazine compound (C2); and an inorganic filler (D), wherein the content of the polyphenylene ether compound (A) is 1 part by mass or more and less than 50 parts by mass relative to 100 parts by mass of the total of the polyphenylene ether compound (A) and the polyphenylene ether compound (B).

[0198] The resin composition of the second technical solution In the resin composition of the first technical solution, the reactive compound (C) contains at least one selected from the group consisting of a maleimide compound having a biphenyl aralkyl structure, a maleimide compound having a phenylmaleimide group, a maleimide compound having an alkyl group with more than 6 carbon atoms, a maleimide compound having an alkylene group with more than 6 carbon atoms, and a maleimide compound having an alkyl group with more than 6 carbon atoms and an alkylene group with more than 6 carbon atoms.

[0199] The resin composition of the third invention is the resin composition of the first or second invention, wherein the content of the polyphenylene ether compound (A) is 0.1 to 45 parts by mass based on 100 parts by mass of the total of the polyphenylene ether compound (A), the polyphenylene ether compound (B) and the reactive compound (C).

[0200] The resin composition of the fourth technical solution is the resin composition of any one of the first to third technical solutions, wherein the content of the polyphenylene ether compound (B) is 10 to 70 parts by mass relative to 100 parts by mass of the total of the polyphenylene ether compound (A), the polyphenylene ether compound (B) and the reactive compound (C).

[0201] The resin composition of the fifth technical solution is the resin composition of any one of the first to fourth technical solutions, wherein the content of the reactive compound (C) is 10 to 80 parts by mass relative to 100 parts by mass of the total of the polyphenylene ether compound (A), the polyphenylene ether compound (B) and the reactive compound (C).

[0202] The resin composition of the sixth technical solution is the resin composition of any one of the first to fifth technical solutions, wherein the inorganic filler (D) is 10 to 250 parts by mass based on 100 parts by mass of the total of the polyphenylene ether compound (A), the polyphenylene ether compound (B) and the reactive compound (C).

[0203] The resin composition according to a seventh aspect is the resin composition according to any one of the first to sixth aspects, wherein the reactive compound (C) contains a maleimide compound (C1) and a benzoxazine compound (C2).

[0204] The resin composition according to an eighth aspect is the resin composition according to any one of the first to seventh aspects, wherein the benzoxazine compound (C2) contains a benzoxazine compound (C2-1) having an alkenyl group.

[0205] A prepreg according to a ninth technical solution comprises: the resin composition according to any one of the first to eighth technical solutions or a semi-cured product of the resin composition; and a fibrous base material.

[0206] A resin-attached film according to a tenth invention comprises: a resin layer comprising the resin composition according to any one of the first to eighth inventions or a semi-cured product of the resin composition; and a support film.

[0207] The resin-coated metal foil according to the eleventh invention comprises: a resin layer including the resin composition according to any one of the first to eighth inventions or a semi-cured product of the resin composition; and a metal foil.

[0208] A metal foil-clad laminate according to a twelfth invention comprises: an insulating layer comprising a cured product of the resin composition according to any one of the first to eighth inventions; and a metal foil.

[0209] A metal foil-clad laminate according to a thirteenth invention comprises: an insulating layer formed of a cured product of the prepreg according to the ninth invention; and a metal foil.

[0210] A wiring board according to a fourteenth invention comprises: an insulating layer formed of a cured product of the resin composition according to any one of the first to eighth inventions; and wiring.

[0211] A wiring board according to a fifteenth invention includes: an insulating layer made of a cured product of the prepreg according to the ninth invention; and wirings.

[0212] 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.

[0213] Example

[0214] [Examples 1 to 12 and Comparative Examples 1 to 6]

[0215] First, the components used to prepare the prepreg in this example will be described.

[0216] (Polyphenylene ether compound (A))

[0217] PPE: a polyphenylene ether compound having a hydroxyl group in the molecule (SA90 manufactured by SABIC Innovative Plastics, 2 terminal hydroxyl groups, number average molecular weight Mn1700, phenol equivalent (hydroxyl equivalent) 850 g / eq)

[0218] (Polyphenylene ether compound (B))

[0219] Modified PPE: a polyphenylene ether compound (styrene-modified polyphenylene ether) having a vinylbenzyl group (vinylbenzyl) at a molecular terminal (OPE-1200 manufactured by Mitsubishi Gas Chemical Co., Ltd., number average molecular weight Mn 1200, functional group equivalent of vinylbenzyl group 670 g / eq)

[0220] (Reactive compound (C))

[0221] Maleimide compound 1: Biphenyl aralkyl type bismaleimide compound (MIR-3000-70MT manufactured by Nippon Kayaku Co., Ltd., bismaleimide compound, maleimide functional group equivalent 275 g / eq)

[0222] Maleimide compound 2: 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide (BMI-5100 manufactured by Nippon Kayaku Co., Ltd., bismaleimide compound, maleimide functional group equivalent 221 g / eq)

[0223] Maleimide compound 3: a maleimide compound having an alkyl group having 6 or more carbon atoms and an alkylene group having 6 or more carbon atoms (BMI-689 manufactured by Designer Molecular Co., Ltd.)

[0224] Benzoxazine compound 1: 3,3'-(methylene-1,4-diphenylene)bis(3,4-dihydro-2H-1,3-benzoxazine) (Pd-type benzoxazine compound manufactured by Shikoku Chemical Industry Co., Ltd., benzoxazine functional group equivalent 217 g / eq)

[0225] Benzoxazine compound 2: a benzoxazine compound having an allyl group as an alkenyl group in the molecule (represented by the above formula (14) and X is a methylene group, R 45 and R 46 A benzoxazine compound in which q and r are 1 (ALP-d type benzoxazine compound manufactured by Shikoku Chemical Industry Co., Ltd., benzoxazine functional group equivalent 244 g / eq))

[0226] (Inorganic filler (D))

[0227] SC2300-SVJ: Spherical silica surface-treated with vinyl silane (SC2300-SVJ manufactured by Admatechs Company Limited)

[0228] (Curing accelerator)

[0229] 2E4MZ: Imidazole curing accelerator (2-ethyl-4-methylimidazole, 2E4MZ manufactured by Shikoku Chemical Industry Co., Ltd.)

[0230] (Preparation method)

[0231] The components other than the inorganic filler are added to methyl ethyl ketone (MEK) in a manner such that the solid content concentration is 60% by mass according to the composition (mass parts) described in Table 1, and stirred and mixed using a disperser to make it uniform. The inorganic filler is added to the uniform mixture according to the composition (mass parts) described in Table 1, and stirred and mixed using a disperser for 2 hours to make it uniform. By doing so, a varnish-like resin composition (varnish) is obtained.

[0232] Next, a prepreg and an evaluation substrate 1 (metal foil-clad laminate) were obtained as follows.

[0233] After impregnating the obtained varnish into a fibrous substrate (glass cloth: "2116 type cloth" manufactured by Nitto Bo Co., Ltd.), it was heated and dried at 150°C using a non-contact heating device. Thus, the solvent in the varnish was removed and the resin composition was semi-cured, thereby obtaining a prepreg (340 mm×510 mm). At this time, the content (resin content) of the components constituting the resin composition by the curing reaction was adjusted to 47% by mass relative to the prepreg.

[0234] Next, an evaluation substrate 1 (metal foil-clad laminate) was obtained in the following manner.

[0235] Six sheets of each of the obtained prepregs were stacked, and copper foil (Mitsui Mining & Smelting Co., Ltd., 35 μm thick, ST foil, one side surface is rough) was arranged on both sides, and the rough surface was located on the prepreg side. It was used as a pressed body and heated and pressed at 200°C, 90 minutes, and a pressure of 2.94 MPa to obtain a copper-clad laminate (evaluation substrate 1: metal-clad laminate) with a thickness of about 0.6 mm and copper foil bonded to both sides.

[0236] A copper-clad laminate having a thickness of about 0.8 mm and copper foil bonded to both surfaces was obtained in the same manner as the evaluation substrate 1 except that the number of prepreg sheets used was changed to 8 (evaluation substrate 2: metal foil-clad laminate).

[0237] A copper-clad laminate having a thickness of about 0.1 mm and copper foil bonded to both surfaces was obtained in the same manner as the evaluation substrate 1 except that the number of prepreg sheets used was changed to one (evaluation substrate 3: metal foil-clad laminate).

[0238] Evaluation substrates 1 to 3 (copper-clad laminates) prepared as described above were evaluated by the methods shown below.

[0239] [Desmearing property]

[0240] First, the copper foil on the surface of the evaluation substrate 1 (copper-clad laminate) was removed by etching. As a desmearing step, the substrate from which the copper foil was removed was immersed in a swelling solution (Swelling Dip Securiganth P manufactured by Atotech Japan Co., Ltd.) at 60°C for 5 minutes, and then immersed in an aqueous potassium permanganate solution (Concentrate Compact CP manufactured by Atotech Japan Co., Ltd.) at 80°C for 10 minutes, and then neutralized. Before and after the desmearing step, the weight of each substrate was measured, and the weight reduced by the desmearing step was calculated (the weight of the substrate before the desmearing step - the weight of the substrate after the desmearing step), and further, based on the reduced weight, the weight per 1 mm 2 Weight loss (mg / mm 2 ). Based on this every 1mm 2 The weight reduction was evaluated as follows.

[0241] If every 1mm 2 The weight loss is less than 15mg / mm 2 , the evaluation is "A (×)", if it is 15mg / mm 2 More than and less than 30mg / mm 2 , the evaluation is "B (○)", if 30mg / mm 2 More than and less than 45mg / mm 2 , the evaluation is "C (◎)", if it is 45mg / mm 2 If the value is greater than or equal to 0, the evaluation is "D (×)".

[0242] It should be noted that "A (×)" is not preferred from the viewpoint of difficulty in removing desmear, and "D (×)" is not preferred from the viewpoint of not being able to maintain the shape of the through hole, etc., because the resin is removed excessively. In contrast, "B (○)" and "C (◎)" are preferred from the viewpoint of being able to remove desmear while maintaining the shape of the through hole, etc., and from this point of view, "C (◎)" is more preferred.

[0243] [Relative dielectric constant (Dk)]

[0244] The bare board from which the copper foil was removed from the evaluation substrate 2 (copper-clad laminate) by etching was used as a test piece, and the relative dielectric constant (Dk) at 1 GHz was measured by the resonant cavity perturbation method. Specifically, the relative dielectric constant (Dk) of the bare board (the insulating layer of the evaluation substrate 2) at 1 GHz was measured according to IPC-TM-6502.5.5.9 using the "Impedance / Material Analyzer 4291A" manufactured by Hewlett-Packard. It should be noted that the relative dielectric constant is good if it is 3.4 or less.

[0245] [Glass transition temperature (Tg)]

[0246] The bare board from which the copper foil was removed from the evaluation substrate 2 (copper-clad laminate) by etching was used as a test piece, and the glass transition temperature (Tg) of the bare board (the insulating layer of the evaluation substrate 2) was measured using a viscoelasticity spectrometer "DMS6100" manufactured by Seiko Instruments Inc. At this time, a dynamic viscoelasticity measurement (DMA) was performed in a bending module with a frequency of 10 Hz, and the temperature at which tanδ showed a maximum when the temperature was raised from room temperature to 280°C at a heating rate of 5°C / min was set as the glass transition temperature Tg (°C). It should be noted that the glass transition temperature is good if it is 240°C or above.

[0247] [Peel strength]

[0248] The copper foil was peeled off from the evaluation substrate 3, and the peel strength at that time was measured according to JIS C 6481. Specifically, the copper foil was peeled off from the evaluation substrate 3 at a speed of 50 mm / min using a tensile tester, and the peel strength (N / mm) at that time was measured.

[0249] Table 1 shows the results of the above evaluation.

[0250]

[0251] As can be seen from Table 1, when the resin composition contains: a polyphenylene ether compound (A) having a hydroxyl group in the molecule; a polyphenylene ether compound (B) having an unsaturated double bond in the molecule; a reactive compound (C) containing at least one selected from a maleimide compound (C1) and a benzoxazine compound (C2); and an inorganic filler (D), wherein the content of the polyphenylene ether compound (A) is 1 part by mass or more and less than 50 parts by mass relative to a total of 100 parts by mass of the polyphenylene ether compound (A) and the polyphenylene ether compound (B) (Examples 1 to 12), a cured product having low dielectric properties, excellent desmear properties and peel strength and a high glass transition temperature can be obtained.

[0252] In contrast, it is known that when the polyphenylene ether compound (A) is not contained (Comparative Example 1), the desmearing property is poor. In addition, it is known that when the polyphenylene ether compound (B) is not contained (Comparative Example 2), the peel strength is low and the desmearing property is poor. In addition, it is known that when the reactive compound (C) is not contained (Comparative Example 3), the glass transition temperature is reduced.

[0253] It is found that even if the polyphenylene ether compound (A) and the polyphenylene ether compound (B) are contained, when the content of the polyphenylene ether compound (A) is 50 parts by mass or more relative to 100 parts by mass of the total of the polyphenylene ether compound (A) and the polyphenylene ether compound (B) (Comparative Examples 4 to 6), the desmearing property is poor.

[0254] According to the comparison of the above-mentioned Comparative Examples 1, 2 and Comparative Examples 4 to 6 with Examples 1 to 12 (especially Examples 1 to 3 and Example 5), it can be seen that the content of the polyphenylene ether compound (A) needs to be 1 part by mass or more and less than 50 parts by mass relative to the total of 100 parts by mass of the polyphenylene ether compound (A) and the polyphenylene ether compound (B).

[0255] Furthermore, from the comparison between Examples 3 and 4, it is found that when the benzoxazine (C2) contains a benzoxazine compound (C2-1) having an alkenyl group (Example 4), a cured product having better peel strength and a higher glass transition temperature can be obtained.

[0256] In addition, by comparing Examples 8 to 10 and 12, it can be seen that when the reactive compound (C) contains the maleimide compound (C1-1) and a maleimide compound (C1-2) other than the maleimide compound (C1-1) as the maleimide compound (C1) (Examples 8 and 12), a cured product having an excellent balance of relative dielectric constant, peel strength and glass transition temperature can be obtained.

[0257] This application is based on Japanese patent application No. 2022-115729 filed on July 20, 2022, and the contents are incorporated herein by reference.

[0258] In order to describe the present invention, the present invention has been appropriately and fully described above by referring to specific embodiments and drawings, but it should be recognized that those skilled in the art can easily change and / or improve the above-mentioned 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.

[0259] Industrial Applicability

[0260] 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 polyphenylene ether compound (A) having a hydroxyl group in the molecule; A polyphenylene ether compound (B) having an unsaturated double bond in the molecule; A reactive compound (C) containing at least one selected from a maleimide compound (C1) and a benzoxazine compound (C2); as well as Inorganic filler (D), wherein The content of the polyphenylene ether compound (A) is 1 part by mass or more and less than 50 parts by mass based on 100 parts by mass of the total of the polyphenylene ether compound (A) and the polyphenylene ether compound (B).

2. The resin composition according to claim 1, characterized in that The reactive compound (C) contains at least one selected from the group consisting of a maleimide compound having a biphenylaralkyl structure, a maleimide compound having a phenylmaleimide group, a maleimide compound having an alkyl group with more than 6 carbon atoms, a maleimide compound having an alkylene group with more than 6 carbon atoms, and a maleimide compound having an alkyl group with more than 6 carbon atoms and an alkylene group with more than 6 carbon atoms.

3. The resin composition according to claim 1, characterized in that The content of the polyphenylene ether compound (A) is 0.1 to 45 parts by mass based on 100 parts by mass of the total of the polyphenylene ether compound (A), the polyphenylene ether compound (B), and the reactive compound (C).

4. The resin composition according to claim 1, characterized in that The content of the polyphenylene ether compound (B) is 10 to 70 parts by mass based on 100 parts by mass of the total of the polyphenylene ether compound (A), the polyphenylene ether compound (B), and the reactive compound (C).

5. The resin composition according to claim 1, characterized in that The content of the reactive compound (C) is 10 to 80 parts by mass based on 100 parts by mass of the total of the polyphenylene ether compound (A), the polyphenylene ether compound (B), and the reactive compound (C).

6. The resin composition according to claim 1, characterized in that The inorganic filler (D) is contained in an amount of 10 to 250 parts by mass based on 100 parts by mass of the total of the polyphenylene ether compound (A), the polyphenylene ether compound (B), and the reactive compound (C).

7. The resin composition according to claim 1, characterized in that The reactive compound (C) contains a maleimide compound (C1) and a benzoxazine compound (C2).

8. The resin composition according to claim 1, characterized in that The benzoxazine compound (C2) contains a benzoxazine compound (C2-1) having an alkenyl group.

9. A prepreg, characterized in that include: The resin composition according to any one of claims 1 to 8 or a semi-cured product of the resin composition; as well as Cellulosic substrate.

10. A film with resin, characterized in that include: A resin layer comprising the resin composition according to any one of claims 1 to 8 or a semi-cured product of the resin composition; as well as Support membrane.

11. A metal foil with resin, characterized in that include: A resin layer comprising the resin composition according to any one of claims 1 to 8 or a semi-cured product of the resin composition; as well as Metal foil.

12. A metal foil-clad laminate, characterized in that include: An insulating layer comprising a cured product of the resin composition according to any one of claims 1 to 8; as well as Metal foil.

13. A metal foil-clad laminate, characterized in that include: An insulating layer comprising a cured product of the prepreg according to claim 9; as well as Metal foil.

14. A wiring board, characterized in that include: An insulating layer comprising a cured product of the resin composition according to any one of claims 1 to 8; as well as wiring.

15. A wiring board, characterized in that include: An insulating layer comprising a cured product of the prepreg according to claim 9; as well as wiring.

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