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 pre-reaction product (A) obtained by reacting a polyphenylene ether compound (a1) having a hydroxyl group in the molecule with an acid anhydride (a2) having an acid anhydride group in the molecule in advance; a benzoxazine compound (B) having an alkenyl group in the molecule; and a reactive compound (C) having an unsaturated double bond in the molecule.

Description

Technical Field

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

[0002] For various electronic devices, as the amount of information processing increases, the installation technology of high integration of semiconductor devices, high density of wiring, and multilayering is developing 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] The relative dielectric constant and dielectric loss factor of known polyphenylene ether are low, and the low dielectric properties such as low relative dielectric constant and low dielectric loss factor are excellent, and even in the high frequency band (high frequency region) from the MHz band to the GHz band, the 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, it is preferably used as a substrate material, etc., which is used to constitute an insulating layer of a wiring board possessed by an electronic device utilizing a high-frequency band. As the substrate material containing polyphenylene ether, the resin composition described in, for example, patent document 1, etc. can be cited.

[0004] Patent Document 1 discloses a curable resin composition comprising: a reaction product of polyphenylene ether and an unsaturated carboxylic acid or anhydride; triallyl cyanurate; and a brominated aromatic compound containing at least one imide ring. Patent Document 1 discloses a polyphenylene ether-based resin composition that can maintain the excellent dielectric properties of polyphenylene ether and exhibit excellent flame retardancy, chemical resistance, and heat resistance after curing.

[0005] It is required that substrate materials used for forming insulating layers of wiring boards can produce cured products that have not only low dielectric properties but also excellent heat resistance, adhesion to metal foil, and desmear properties and a high glass transition temperature.

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent document 1: Japanese Patent Publication No. 7-166049 Summary of the invention

[0009] 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, heat resistance, excellent adhesion to metal foil and desmearing property 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.

[0010] One aspect of the present invention relates to a resin composition comprising: a pre-reaction product (A) obtained by pre-reacting a mixture of a polyphenylene ether compound (a1) having a hydroxyl group in the molecule and an acid anhydride (a2) having an acid anhydride group in the molecule; a benzoxazine compound (B) having an alkenyl group in the molecule; and a reactive compound (C) having an unsaturated double bond in the molecule.

[0011] The above and other objects, features and advantages of the present invention will become more apparent from the following detailed description and accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] Figure 1 This is a schematic cross-sectional view showing an example of a prepreg according to an embodiment of the present invention.

[0013] 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.

[0014] Figure 3 This is a schematic cross-sectional view showing an example of a wiring board according to an embodiment of the present invention.

[0015] 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.

[0016] 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

[0017] The metal foil-clad laminate and the metal foil with resin used in manufacturing wiring boards etc. 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. And as the wiring, wiring formed of metal foil etc. that the metal foil-clad laminate etc. have can be cited.

[0018] Electronic devices, especially small mobile devices such as mobile communication terminals and laptop computers, are rapidly developing in terms of diversification, high performance, thinness and miniaturization. Along with this, the wiring boards used in these products are also further required to have miniaturized conductor wiring, multilayered conductor wiring layers, thinness and high performance in mechanical properties. Therefore, it is required that the wiring board will not peel off from the insulating layer even if the wiring it has is miniaturized. In order to meet this requirement, the wiring board is required to have high adhesion between the wiring and the insulating layer. Therefore, for metal foil-clad laminates, 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.

[0019] The insulating layer of the wiring board used in various electronic devices is also required to be able to properly remove the slag (smear) generated by the drilling process when drilling is performed using a drill bit, laser, etc. Specifically, the insulating layer of the wiring board is required to have a performance that can properly remove the smear (excellent desmearing property) while suppressing damage to the insulating layer of the wiring board using permanganate, 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.

[0020] The wiring boards used in various electronic devices are also required to be less susceptible to changes in the external environment. For example, they are required to have excellent heat resistance so that the wiring boards can be used even in a high temperature environment. Therefore, it is required that the substrate material used to form the insulating layer of the wiring board can obtain a cured product with excellent heat resistance. In addition, in order to obtain a wiring board with excellent reliability in a wide temperature range, it is required 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.

[0021] The present inventors have conducted various studies and have found that the above object can be achieved by the present invention, that is, providing a resin composition that can produce a cured product having low dielectric properties, excellent heat resistance, adhesion to metal foil and desmear properties, and a high glass transition temperature.

[0022] Embodiments according to the present invention will be described below, but the present invention is not limited to these embodiments.

[0023] [Resin composition]

[0024] One embodiment of the present invention relates to a resin composition, comprising: a pre-reaction product (A) obtained by pre-reacting a mixture of a polyphenylene ether compound (a1) having a hydroxyl group in the molecule and an acid anhydride (a2) having an acid anhydride group in the molecule; a benzoxazine compound (B) having an alkenyl group in the molecule; and a reactive compound (C) having an unsaturated double bond in the molecule. The resin composition can be cured to obtain a cured product having low dielectric properties, heat resistance, excellent adhesion to metal foil and desmearing properties, and a high glass transition temperature.

[0025] It is believed that the resin composition can be cured well by allowing the pre-reaction product (A) obtained by reacting the mixture containing the polyphenylene ether compound (a1) and the acid anhydride (a2) in advance to cure together with the benzoxazine compound (B) and the reactive compound (C), and can obtain a cured product with a high glass transition temperature, excellent heat resistance, and excellent adhesion to metal foil while maintaining the excellent low dielectric properties of the polyphenylene ether chain in the polyphenylene ether compound (a1). It is believed that if the resin composition contains the acid anhydride (a2), the cured product obtained is easy to remove smear. In addition, it is believed that if the resin composition contains the acid anhydride (a2), the glass transition temperature of the cured product obtained is also increased. On the other hand, if the acid anhydride (a2) is present in the resin composition, the cured product of the resin composition tends to have reduced adhesion to the metal foil. It is believed that: in the resin combination, by reacting the acid anhydride (a2) with the polyphenylene ether compound (a1) in advance, the acid anhydride (a2) is difficult to volatilize and is easily retained in the resin combination. In addition, by reacting the acid anhydride (a2) with the polyphenylene ether compound (a1), it is possible to suppress the situation that the adhesion with the metal foil caused by the presence of the acid anhydride (a2) is reduced. Based on these reasons, it is believed that: the adhesion with the metal foil can be suppressed to be reduced, and the effect of the acid anhydride (a2) can be well brought into play, such as the easy desmearing of the cured product, or the effect of the glass transition temperature of the cured product. Based on these reasons, it is believed that: the resin combination can obtain a cured product with low dielectric properties, heat resistance, excellent adhesion with the metal foil and desmearing and a high glass transition temperature.

[0026] (Pre-reaction product (A))

[0027] The pre-reaction product (A) is not particularly limited as long as it is a pre-reaction product obtained by reacting a mixture of a polyphenylene ether compound (a1) having a hydroxyl group in the molecule and an acid anhydride (a2) having an acid anhydride group in the molecule in advance. The pre-reaction product (A) may be, for example, a product obtained by reacting the polyphenylene ether compound (a1) with the acid anhydride (a2) in advance, or may be a reaction product obtained by reacting with other raw materials (a3) ​​in advance, wherein the other raw materials (a3) ​​are compounds that can react with at least one of the polyphenylene ether compound (a1) and the acid anhydride (a2). That is, the pre-reaction product (A) may include, for example: a reaction product (A1) obtained by reacting the polyphenylene ether compound (a1) with the acid anhydride (a2); and a reaction product (A2) obtained by reacting the polyphenylene ether compound (a1), the acid anhydride (a2) and the other raw materials (a3). In addition, as the mixture, it is sufficient to contain a mixture of the polyphenylene ether compound (a1) and the acid anhydride (a2), or it is sufficient to contain a mixture of the other raw materials (a3). The pre-reaction product (A) may react with the benzoxazine compound (B) and the reactive compound (C). The resin composition is cured by reacting the pre-reaction product (A) with the benzoxazine compound (B) and the reactive compound (C). In the resin composition, as the pre-reaction product (A), it is sufficient to contain at least one of the reaction product (A1) obtained by reacting the polyphenylene ether compound (a1) with the acid anhydride (a2) and the reaction product (A2) obtained by reacting the polyphenylene ether compound (a1), the acid anhydride (a2) and the other raw materials (a3). In the resin composition, the unreacted polyphenylene ether compound (a1) may be contained, the unreacted acid anhydride (a2) may be contained, and the unreacted other raw materials (a3) ​​may be contained. In the resin composition, as the pre-reaction product (A), the reaction product [at least one of the reaction product (A1) and the reaction product (A2)] may be contained, and the polyphenylene ether compound (a1) and the acid anhydride (a2) may also be contained. In addition, the resin composition may also contain the other raw materials (a3). It should be noted that the other raw materials (a3) ​​are not particularly limited as long as they are compounds that can react with at least one of the polyphenylene ether compound (a1) and the acid anhydride (a2).

[0028] (Polyphenylene ether compound (a1))

[0029] The polyphenylene ether compound (a1) is not particularly limited as long as it has a hydroxyl group in the molecule. The polyphenylene ether compound (a1) has a polyphenylene ether chain in the molecule, and preferably has a repeating unit represented by the following formula (1) in the molecule.

[0030]

[0031] 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.

[0032] In R1 to R4, as each functional group listed above, specifically, the following groups can be mentioned.

[0033] The alkyl group is not particularly limited, but is preferably an alkyl group having 1 to 18 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a hexyl group, and a decyl group.

[0034] The alkenyl group is not particularly limited, but is preferably an alkenyl group having 2 to 18 carbon atoms, and more preferably an alkenyl group having 2 to 10 carbon atoms. Specific examples thereof include a vinyl group, an allyl group, and a 3-butenyl group.

[0035] The alkynyl group is not particularly limited, and is preferably an alkynyl group having 2 to 18 carbon atoms, and more preferably an alkynyl group having 2 to 10 carbon atoms. Specific examples thereof include ethynyl and prop-2-yn-1-yl (propargyl).

[0036] The alkylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkyl group, and is preferably an alkylcarbonyl group having 2 to 18 carbon atoms, and more preferably an alkylcarbonyl group having 2 to 10 carbon atoms. Specific examples thereof include acetyl, propionyl, butyryl, isobutyryl, pivaloyl, hexanoyl, octanoyl, and cyclohexylcarbonyl groups.

[0037] The alkenylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkenyl group, and is preferably an alkenylcarbonyl group having 3 to 18 carbon atoms, and more preferably an alkenylcarbonyl group having 3 to 10 carbon atoms. Specific examples thereof include acryloyl, methacryloyl, and crotonoyl groups.

[0038] The alkynylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkynyl group, and for example, an alkynylcarbonyl group having 3 to 18 carbon atoms is preferred, and an alkynylcarbonyl group having 3 to 10 carbon atoms is more preferred. Specific examples include propioloyl and the like.

[0039] The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polyphenylene ether compound (a1) are not particularly limited, and are preferably 500 to 5000, preferably 800 to 4000, and preferably 1000 to 3000. If the molecular weight is too low, there is a tendency that a cured product with sufficient heat resistance cannot be obtained. In addition, if the molecular weight is too high, the melt viscosity of the resin composition becomes high, sufficient fluidity cannot be obtained, and there is a tendency that molding defects cannot be fully suppressed. Therefore, as long as the weight average molecular weight of the polyphenylene ether compound is within the above range, excellent heat resistance and formability of the cured product can be achieved. It should be noted that, here, the weight average molecular weight and the number average molecular weight are values ​​obtained by measuring the weight average molecular weight by a conventional molecular weight measurement method, and specifically, values ​​measured by gel permeation chromatography (GPC) can be cited, for example. In addition, when the polyphenylene ether compound 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 within the range. Specifically, t is preferably 1 to 50.

[0040] The average number of hydroxyl groups (hydroxyl number) in the polyphenylene ether compound (a1) is not particularly limited, and is preferably 1 to 5, more preferably 1.5 to 3. If the number of hydroxyl groups is too small, it is difficult to react with the acid anhydride (a2). In addition, the reactivity of the pre-reaction product obtained by reacting with the acid anhydride (a2) with the benzoxazine compound (B) and the reactivity with the reactive compound (C) are reduced, and there is a tendency that it is difficult to obtain a cured product with sufficient heat resistance. In addition, if the number of hydroxyl groups is too large, the reactivity with the acid anhydride (a2) becomes too high. In addition, the reactivity of the pre-reaction product (A) obtained by reacting with the acid anhydride (a2) with the benzoxazine compound (B) and the reactivity with the reactive compound (C) become too high, and there is a risk of reduced storage of the resin composition.

[0041] It should be noted that the number of hydroxyl groups of the polyphenylene ether compound 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.

[0042] The intrinsic viscosity of the polyphenylene ether compound (a1) 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. If the intrinsic viscosity is too low, there is a tendency for the molecular weight to be low, and there is a tendency for it to be difficult to obtain a cured product with sufficient heat resistance. In addition, if the intrinsic viscosity is too high, the viscosity is high, sufficient fluidity cannot be obtained, and there is a tendency that molding defects cannot be fully suppressed. Therefore, if the intrinsic viscosity of the polyphenylene ether compound (a1) is within the above range, excellent heat resistance and formability of the cured product can be achieved.

[0043] It should be noted that the intrinsic viscosity here can be known from the specification value of the product of the polyphenylene ether compound (a1) 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, AVS500 Visco System manufactured by Schott can be cited.

[0044] The polyphenylene ether compound (a1) is not particularly limited, and examples thereof include polyphenylene ethers including "2,6-dimethylphenol" and "at least one of a bifunctional phenol and a trifunctional phenol", and compounds containing polyphenylene ethers such as poly(2,6-dimethyl-1,4-phenylene ether) as main components. More specifically, examples of the polyphenylene ether compound (a1) include polyphenylene ether compounds represented by the following formula (2) and polyphenylene ether compounds represented by the following formula (3).

[0045]

[0046] 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 ~R 36 , and the same groups as R1 to R4 in the above formula (1) can be mentioned. 20 and R 21 ~R 36represents 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.

[0047] 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).

[0048]

[0049] 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.

[0050] 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.

[0051]

[0052] 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).

[0053] (anhydride (a2))

[0054] The acid anhydride (a2) is not particularly limited as long as it is an acid anhydride with an anhydride group in the molecule. The anhydride group can have a structure of dehydration condensation of carboxylic acids respectively contained in different molecules, or a structure of dehydration condensation of 2 carboxylic acids in the molecule. In addition, the acid anhydride (a2) can be an acid anhydride (monofunctional acid anhydride) with 1 anhydride group in the molecule, or an acid anhydride (polyfunctional acid anhydride) with more than 2 anhydride groups in the molecule. The acid anhydride (a2) preferably contains an acid anhydride with more than 1 cyclic anhydride group in the molecule. In addition, the carbon number of the acid anhydride (a2) is not particularly limited, preferably more than 6, more preferably more than 8, and preferably less than 25, more preferably less than 18.

[0055] The acid anhydride (a2) is not particularly limited, and examples thereof include the monofunctional acid anhydride and the polyfunctional acid anhydride as described above.

[0056] The monofunctional acid anhydride is not particularly limited, and examples thereof include maleic anhydride, phthalic anhydride, succinic anhydride, trimellitic anhydride, a compound represented by the following formula (7), methylbicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, bicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, nadic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, tetrapropenylsuccinic anhydride (3-dodecenylsuccinic anhydride), and octenylsuccinic anhydride.

[0057]

[0058] In formula (7), R A represents a hydrogen atom or an alkyl group. The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, and more preferably a methyl group. A A hydrogen atom is also preferred. A It is preferably a hydrogen atom or a methyl group. A The compound in which R is methyl is 4-methylhexahydrophthalic anhydride. A The compound containing hydrogen atoms is hexahydrophthalic anhydride.

[0059] The polyfunctional acid anhydride is not particularly limited, and examples thereof include 1,2,3,4-butanetetracarboxylic dianhydride, ethylene glycol trimellitic anhydride, glycerol trimellitic anhydride monoacetate, 1,3,3a,4,5,9b-hexahydro-5 (tetrahydro-2,5-dioxo-3-furidyl) naphtho [1,2-C] furan-1,3-dione, pyromellitic anhydride, and benzophenonetetracarboxylic anhydride.

[0060] As the acid anhydride, a commercially available product can also be used. As succinic anhydride, for example, RIKACID SA manufactured by New Japan Chemical Co., Ltd. can be used. In addition, as 4-methylhexahydrophthalic anhydride, for example, RIKACID MH manufactured by New Japan Chemical Co., Ltd. can be used. In addition, as hexahydrophthalic anhydride, for example, RIKACID HH manufactured by New Japan Chemical Co., Ltd. can be used. In addition, as 1,2,3,6-tetrahydrophthalic anhydride, for example, RIKACID TH manufactured by New Japan Chemical Co., Ltd. can be used. In addition, as tetrapropylene succinic anhydride (3-dodecenyl succinic anhydride), for example, RIKACID DDSA manufactured by New Japan Chemical Co., Ltd. can be used. In addition, as octenyl succinic anhydride, for example, RIKACID OSA manufactured by New Japan Chemical Co., Ltd. can be used. In addition, as a mixture of methylbicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride and bicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, for example, RIKACID HNA-100 manufactured by New Japan Chemical Industry Co., Ltd. can be used. In addition, as a mixture of 4-methylhexahydrophthalic anhydride and hexahydrophthalic anhydride (mass ratio 70:30), for example, RIKACID MH-700 manufactured by New Japan Chemical Industry Co., Ltd. can be used. In addition, as 1,2,3,4-butanetetracarboxylic dianhydride, for example, RIKACID BT-100 manufactured by New Japan Chemical Industry Co., Ltd. can be used. In addition, as ethylene glycol bis(trimellitic anhydride), for example, RIKACID TMEG-100, RIKACID TMEG-500, RIKACID TMEG-600 and RIKACID TMEG-S manufactured by New Japan Chemical Industry Co., Ltd. can be used. In addition, as glyceryl bis(trimellitate) monoacetate, for example, RIKACID TMTA-C manufactured by Shin Nippon Rika Co., Ltd. can be used. In addition, as 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furyl)naphtho[1,2-c]furan-1,3-dione, for example, RIKACID TDA-100 manufactured by Shin Nippon Rika Co., Ltd. can be used.

[0061] The acid anhydride (a2) may be used alone or in combination of two or more.

[0062] (catalyst)

[0063] A catalyst can be used in the reaction. As the catalyst, there is no particular limitation as long as it is a catalyst that helps promote the reaction between the polyvinyl ether compound (a1) and the acid anhydride (a2). The catalyst can also be a catalyst that not only helps promote the reaction between the polyvinyl ether compound (a1) and the acid anhydride (a2), but also helps promote the reaction between the polyvinyl ether compound (a1) and the other raw materials (a3), and / or the reaction between the acid anhydride (a2) and the other raw materials (a3). As the catalyst, for example, 2-ethyl-4-methylimidazole (2E4MZ) etc. can be mentioned.

[0064] (Reaction Product)

[0065] In the resin composition, as the pre-reaction product (A), at least one of the reaction product (A1) obtained by reacting the polyphenylene ether compound (a1) with the acid anhydride (a2) and the reaction product (A2) obtained by reacting the polyphenylene ether compound (a1), the acid anhydride (a2) and the other raw materials (a3) ​​is contained. In these reactions, the hydroxyl group of the polyphenylene ether compound (a1) acts on the anhydride group of the acid anhydride (a2), and the anhydride group is ring-opened to form an ester bond. That is, the reaction product has an ester bond in the molecule. In addition, in this reaction, a carboxyl group is generated by ring-opening of the anhydride group. For these reasons, if the reaction proceeds well, an ester and a carboxyl-modified polyphenylene ether compound having an ester bond and a carboxyl group in the molecule can be obtained. Therefore, the pre-reaction product (A) preferably contains an ester and a carboxyl-modified polyphenylene ether compound whose terminal is modified by a substituent having one or more ester bonds and one or more carboxyl groups. That is, examples of the resin composition include a resin composition containing the ester and carboxyl-modified polyphenylene ether compound, the benzoxazine compound (B), and the reactive compound (C).

[0066] The reaction product is not particularly limited as long as it is at least one of a reaction product (A1) obtained by reacting the polyphenylene ether compound (a1) with the acid anhydride (a2) and a reaction product (A2) obtained by reacting the polyphenylene ether compound (a1), the acid anhydride (a2) and the other raw materials (a3), and examples thereof include: a compound obtained by reacting the compound represented by the formula (7) as the acid anhydride (a2) with the polyphenylene ether compound (a1); and a compound obtained by reacting octenyl succinic anhydride as the acid anhydride (a2) with the polyphenylene ether compound (a1). In addition, the compound obtained by reacting the compound represented by the formula (7) as the acid anhydride (a2) with the polyphenylene ether compound (a1) varies depending on the structure of the polyphenylene ether compound (a1), and examples thereof include a compound represented by the following formula (8).

[0067]

[0068] In formula (8), R A Examples include the same groups as R in formula (7), and specifically, it represents a hydrogen atom or an alkyl group. 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 each preferably represent 0 to 20.

[0069] The equivalent ratio of the anhydride group of the acid anhydride (a2) to the hydroxyl group of the polyphenylene ether compound (a1) (anhydride group of the acid anhydride (a2) / hydroxyl group of the polyphenylene ether compound (a1)) is preferably 1.5 or less, more preferably 0.3 to 1.5, and further preferably 0.8 to 1. That is, when the amount of the hydroxyl group of the polyphenylene ether compound (a1) is 1 equivalent, the amount of the anhydride group of the acid anhydride (a2) is preferably 1.5 equivalents or less, more preferably 0.3 to 1.5 equivalents, and further preferably 0.8 to 1 equivalent. If the polyphenylene ether compound (a1) is too much, the polyphenylene ether compound (a1) remains too much, and if the acid anhydride (a2) is too much, the acid anhydride (a2) remains too much, and there is a tendency that it is difficult to obtain a suitable preliminary reaction product. Therefore, by mixing the polyphenylene ether compound (a1) and the acid anhydride (a2) in the equivalent ratio range, a suitable pre-reaction product can be obtained, and a resin composition and a cured product thereof with excellent performance can be obtained. It should be noted that the equivalent is a relative value based on the reactive functional group, and the hydroxyl equivalent of the polyphenylene ether compound can also be defined as a phenol equivalent.

[0070] The conditions of the reaction are not particularly limited as long as the reaction proceeds. As the conditions of the reaction, for example, the conditions that the ring opening rate of the acid anhydride (a2) is 80 to 100% are preferred. In the pre-reaction, the acid anhydride (a2) is ring-opened by reacting with the polyphenylene ether compound (a1) as described above. Therefore, the degree of progress of the reaction can be confirmed by the ring opening rate of the acid anhydride (a2). In the pre-reaction product, it is preferred that the ring opening rate of the acid anhydride (a2) is 80 to 100% as described above. Accordingly, the acid anhydride (a2) remaining in the pre-reaction product (A) decreases, and the adverse effects caused by the acid anhydride (a2) can be reduced. If the ring opening rate of the acid anhydride (a2) is too low, the unreacted acid anhydride (a2) remains more, and the acid anhydride (a2) is easily volatilized and disappears during the manufacturing process of the prepreg. As a result, it is believed that the curing component is insufficient, so that the crosslinking degree of the cured product of the resin composition is reduced, and there is a tendency for the glass transition temperature of the cured product to decrease.

[0071] The ring-opening rate of the acid anhydride (a2) can be calculated, for example, by comparing the infrared absorption spectra of the mixture before and after the reaction. The mixture may have a peak at 1800 to 1900 cm due to the cyclic acid anhydride group before and after the reaction (pre-reaction). -1 In addition, the mixture may have a peak at 1450-1580 cm caused by the benzene ring that does not participate in the reaction. -1 The peak near the benzene ring. Then, the peak caused by the benzene ring is used as an internal standard to obtain the amount (relative value) of the peak caused by the anhydride group before and after the reaction. The amount of the peak is obtained according to the area ratio using the internal standard. Specifically, the area (A1) of the peak caused by the anhydride group before the reaction, the area (A2) of the peak caused by the anhydride group after the reaction, the area (B1) of the peak caused by the benzene ring before the reaction, and the area (B2) of the peak caused by the benzene ring after the reaction are used. At this time, the area ratio (A1 / B1) is the amount of the anhydride group before the reaction, and the area ratio (A2 / B2) is the amount of the anhydride group after the reaction. Substitute them into the following formula.

[0072] Opening rate (%) = {1-(A2 / B2) / (A1 / B1)}×100

[0073] Thereby, the ring-opening rate of the acid anhydride can be calculated.

[0074] It should be noted that, since the ring-opening rate of the acid anhydride (a2) varies depending on the heating temperature and heating time when preparing the varnish, it is preferred to appropriately adjust the heating conditions so that the ring-opening rate is as high as possible, and more preferably to appropriately adjust the heating conditions so that the ring-opening rate is 80% or more. The conditions of the preliminary reaction can be appropriately set by sampling the reaction product over time while performing the preliminary reaction and confirming the ring-opening rate.

[0075] The conditions of the reaction can be listed as the above conditions, and more specifically, the reaction temperature is preferably 30 to 100°C, and more preferably 60 to 80°C. If the reaction temperature is too low, there is a tendency for the reaction to be difficult to proceed. In addition, if the reaction temperature is too high, there is a risk that the acid anhydride (a2) will volatilize before the acid anhydride (a2) reacts with the polyphenylene ether compound (a1). Therefore, if the reaction temperature is within the above range, the polyphenylene ether compound (a1) and the acid anhydride (a2) can react well. In addition, the reaction time is preferably 2 to 10 hours, and more preferably 3 to 6 hours. If the reaction time is within the above range, the polyphenylene ether compound (a1) and the acid anhydride (a2) can react well.

[0076] (Benzoxazine compound (B))

[0077] The benzoxazine compound (B) is not particularly limited as long as it is a benzoxazine compound having an alkenyl group in the molecule. It should be noted that the benzoxazine compound (B) is a compound having a benzoxazine group in the molecule, and also includes benzoxazine resins, etc. That is, the benzoxazine compound (B) is a compound having an alkenyl group and a benzoxazine group in the molecule, and examples thereof include compounds having a benzoxazine group in the molecule and the benzoxazine group having an alkenyl group, etc. It should be noted that the benzoxazine compound (B) is a compound different from the reactive compound (C). The alkenyl group is not particularly limited, and examples thereof include alkenyl groups having 2 to 6 carbon atoms, etc. As the alkenyl group, specifically, vinyl, allyl and butenyl groups, etc., can be cited, among which allyl groups are preferred. In addition, as the benzoxazine compound (B), for example, compounds having a benzoxazine group (the benzoxazine group having an alkenyl group) in the molecule, etc. can be cited. Examples of the benzoxazinyl group (benzoxazinyl group having an alkenyl group) include, for example, a benzoxazinyl group represented by the following formula (9) and a benzoxazinyl group represented by the following formula (10). Examples of the benzoxazinyl compound (B) include, for example, a benzoxazinyl compound having a benzoxazinyl group represented by the following formula (9) in the molecule, a benzoxazinyl compound having a benzoxazinyl group represented by the following formula (10) in the molecule, and a benzoxazinyl compound having a benzoxazinyl group represented by the following formula (9) and a benzoxazinyl group represented by the following formula (10) in the molecule. Examples of the benzoxazinyl compound having a benzoxazinyl group represented by the following formula (9) in the molecule include, for example, a benzoxazinyl compound represented by the following formula (11).

[0078]

[0079] In formula (9), R 39 represents an alkenyl group, and p represents 1 to 4. p is R 39 The average value of the degree of substitution is 1 to 4, preferably 1.

[0080]

[0081] In formula (10), R 40 It represents an alkenyl group.

[0082]

[0083] In formula (11), R 41 and R 42 Each independently represents an alkenyl group, X represents an alkylene group, and q and r each independently represent 1 to 4. That is, q and r may be the same or different, and each represents 1 to 4.

[0084] The alkenyl group in the formulae (9) to (11) is not particularly limited as described above, but is preferably an allyl group.

[0085] The alkylene group is not particularly limited, and examples thereof include methylene, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octyl, eicosyl, hexatriacontyl, etc. Among them, methylene is preferred.

[0086] q is R 41 The average substitution degree of is 1 to 4, preferably 1. 42 The average value of the degree of substitution is 1 to 4, preferably 1.

[0087] As the benzoxazine compound (B), a commercially available product may be used, and for example, ALPd manufactured by Shikoku Chemicals Co., Ltd. may be used.

[0088] As the benzoxazine compound (B), the benzoxazine compounds exemplified above may be used alone or in combination of two or more.

[0089] (Reactive compound (C))

[0090] The reactive compound (C) is not particularly limited as long as it is a reactive compound having an unsaturated double bond in the molecule. It should be noted that the reactive compound (C) is a compound that reacts with at least one of the pre-reaction product (A) and the benzoxazine compound (B). In addition, the reactive compound (C) is a compound different from the benzoxazine compound (B). That is, the reactive compound (C) is a reactive compound having an unsaturated double bond in the molecule other than the benzoxazine compound (B). In addition, the resin composition is a resin composition containing the pre-reaction product (A), the benzoxazine compound (B), and a reactive compound (C) having an unsaturated double bond in the molecule other than the benzoxazine compound (B). As the reactive compound (C), for example, unsaturated double bond-modified polyphenylene ether compounds, allyl compounds, acrylate compounds, methacrylate compounds, vinyl compounds such as polybutadiene compounds and styrene compounds, and maleimide compounds, etc., which are modified by substituents having unsaturated double bonds at the ends, can be cited. As for the reactive compound (C), the unsaturated double bond-modified polyphenylene ether compounds and maleimide compounds are preferred among these. That is, the reactive compound (C) preferably contains at least one selected from the group consisting of the unsaturated double bond-modified polyphenylene ether compounds and the maleimide compounds.

[0091] The unsaturated double-bond modified polyphenylene ether compound is not particularly limited as long as it is a modified polyphenylene ether compound whose terminal is modified by a substituent having an unsaturated double bond. As the unsaturated double-bond modified polyphenylene ether compound, for example, a compound in which the polyphenylene ether compound (a1) is terminally modified by a substituent having an unsaturated double bond, etc., more specifically, a polyphenylene ether compound (styrene-modified polyphenylene ether) having a vinylbenzyl group (vinylbenzyl) at a molecular terminal, a polyphenylene ether compound (acryloyl-modified polyphenylene ether) having an acryloyl group at a molecular terminal, and a polyphenylene ether compound (methacryloyl-modified polyphenylene ether) having a methacryloyl group at a molecular terminal, etc. can be cited.

[0092] 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).

[0093] 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.

[0094] 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).

[0095] 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.

[0096] The maleimide compound is not particularly limited as long as it is a compound having a maleimide group in the molecule. Examples of the maleimide compound include: a monofunctional maleimide compound having one maleimide group in the molecule, a polyfunctional maleimide compound having two or more maleimide groups in the molecule, and a modified maleimide compound. Examples of the modified maleimide compound include: a modified maleimide compound in which a part of the molecule is modified by an amine compound, a modified maleimide compound in which a part of the molecule is modified by an organosilicon compound, and a modified maleimide compound in which a part of the molecule is modified by an amine compound and an organosilicon compound.

[0097] As the maleimide compound, for example, a maleimide compound having a phenylmaleimide group in the molecule; a maleimide compound containing at least one of an alkyl group with a carbon number of 6 or more and an aralkyl group with a carbon number of 6 or more in the molecule (a maleimide compound having an alkyl group with a carbon number of 6 or more in the molecule, a maleimide compound having an aralkyl group with a carbon number of 6 or more in the molecule, a maleimide compound having an alkyl group with a carbon number of 6 or more and an aralkyl group with a carbon number of 6 or more in the molecule); a maleimide compound having a biphenyl aralkyl structure in the molecule (a biphenyl aralkyl type maleimide compound); and 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, etc. From the viewpoint of being able to obtain a resin composition that becomes a cured product with a lower relative dielectric constant and a higher glass transition temperature, it is preferred to use these maleimide compounds.

[0098] As the maleimide compound having a phenylmaleimide group in the molecule, there can be listed: 4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, metaphenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide; and a maleimide compound having a phenylmaleimide group and an arylene structure substituted at the meta position in the molecule, etc. It should be noted that the arylene structure bonded in a directional manner at the meta position is an arylene group bonded in a directional manner at the meta position, and for example, metaphenylene and metanaphthylene and other metaarylene groups can be listed.

[0099] As the maleimide compound, a commercially available product can be used. Specifically, as 4,4'-diphenylmethane bismaleimide, for example, BMI-1000 manufactured by Yamato Chemicals Co., Ltd. can be used. In addition, as polyphenylmethane maleimide, for example, BMI-2300 manufactured by Yamato Chemicals Co., Ltd. can be used. In addition, as metaphenylene bismaleimide, for example, BMI-3000 manufactured by Yamato Chemicals Co., Ltd. can be used. In addition, as bisphenol A diphenyl ether bismaleimide, for example, BMI-4000 manufactured by Yamato Chemicals Co., Ltd. can be used. In addition, as 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, for example, BMI-5100 manufactured by Yamato Chemicals Co., Ltd. can be used. In addition, as 4-methyl-1,3-phenylene bismaleimide, for example, BMI-7000 manufactured by Yamato Chemical Industry Co., Ltd. can be used. In addition, as 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, for example, BMI-TMH manufactured by Yamato Chemical Industry Co., Ltd. can be used. In addition, as a biphenyl aralkyl type maleimide compound, for example, MIR-3000-70T manufactured by Nippon Kayaku Co., Ltd. can be used.

[0100] The reactive compound (C) may be used alone or in combination of two or more.

[0101] From the viewpoint of being able to obtain a resin composition having a higher glass transition temperature, the reactive compound (C) preferably contains at least one (C1) selected from the biphenyl aralkyl maleimide compound and the polyphenylmethane maleimide [the first maleimide compound (C1)]. The reactive compound (C) more preferably contains the first maleimide compound (C1) and a reactive compound (C2) other than the first maleimide compound (C1) in the reactive compound (C) [another reactive compound (C2)]. Furthermore, the other reactive compound (C2) preferably contains a maleimide compound (C3) other than the first maleimide compound (C1) [the second maleimide compound (C3)] and the unsaturated double bond-modified polyphenylene ether compound [hereinafter referred to as the unsaturated double bond-modified polyphenylene ether compound (C4)]. That is, the reactive compound (C) further preferably contains the first maleimide compound (C1), the second maleimide compound (C3) and the unsaturated double bond modified polyphenylene ether compound (C4). The maleimide compound (C3) is preferably, for example, 3,3-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide. If the reactive compound (C) contains the second maleimide compound (C3) [that is, the reactive compound (C) contains not only the first maleimide compound (C1) but also the second maleimide compound (C3)], then in the cured product of the obtained resin composition, the uniformity of the contained components can be further improved, and a more suitable cured product can be obtained.

[0102] When the reactive compound (C) contains the first maleimide compound (C1) and the other reactive compound (C2), the content of the first maleimide compound (C1) is preferably 5 to 80 parts by mass, and more preferably 10 to 70 parts by mass, relative to 100 parts by mass of the reactive compound (C) [relative to 100 parts by mass of the total mass of the first maleimide compound (C1) and the other reactive compound (C2)].

[0103] When the reactive compound (C) contains the first maleimide compound (C1) and the other reactive compound (C2), and the other reactive compound (C2) contains the second maleimide compound (C3) and the unsaturated double bond-modified polyphenylene ether compound (C4), the content of the first maleimide compound (C1) is preferably 10 to 80 parts by mass, and more preferably 25 to 60 parts by mass, relative to 100 parts by mass of the total mass of the first maleimide compound (C1) and the second maleimide compound (C3). Furthermore, the content of the unsaturated double bond-modified polyphenylene ether compound (C4) is preferably 5 to 70 parts by mass, more preferably 10 to 65 parts by mass, relative to 100 parts by mass of the total mass of the first maleimide compound (C1), the second maleimide compound (C3), and the unsaturated double bond-modified polyphenylene ether compound (C4) [relative to 100 parts by mass of the total mass of the first maleimide compound (C1) and the other reactive compound (C2)].

[0104] When the first maleimide compound (C1) is too little, there is a tendency that the effect of using the first maleimide compound (C1) and the second maleimide compound (C3) can not be fully exerted. Specifically, in the cured product of the obtained resin composition, there is a tendency that the above-mentioned effect of the uniformity of the contained components cannot be fully exerted. In addition, the situation that the first maleimide compound (C1) is too much, the situation that the second maleimide compound (C3) is too little, and the situation that the second maleimide compound (C3) is too much are also the same as the situation that the first maleimide compound (C1) is too little. Specifically, in these cases, in the cured product of the obtained resin composition, there is also a tendency that the above-mentioned effect of the uniformity of the contained components cannot be fully exerted. If the unsaturated double bond modified polyphenylene ether compound (C4) is too little, there is a tendency that it is difficult to maintain low dielectric properties. In addition, if the unsaturated double-bond modified polyphenylene ether compound (C4) is too much, the total amount of the first maleimide compound (C1) and the second maleimide compound (C3) is too small, and there is a tendency that the effect of using the first maleimide compound (C1) and the second maleimide compound (C3) in combination cannot be fully exerted. Based on these reasons, by containing the first maleimide compound (C1), the second maleimide compound (C3) and the unsaturated double-bond modified polyphenylene ether compound (C4) in a manner within the above-mentioned respective ranges, a resin composition is obtained by using a cured product having low dielectric properties, heat resistance, excellent adhesion to metal foil and desmearing properties and a high glass transition temperature as a cured product with higher uniformity.

[0105] (content)

[0106] The content of the pre-reaction product (A) is not particularly limited, and is preferably 1 to 40 parts by mass, more preferably 3 to 40 parts by mass, and further preferably 5 to 30 parts by mass, relative to 100 parts by mass of the total of the pre-reaction product (A), the benzoxazine compound (B), and the reactive compound (C). That is, the total content of the benzoxazine compound (B) and the reactive compound (C) is not particularly limited, and is 60 to 99 parts by mass, preferably 60 to 97 parts by mass, and more preferably 70 to 95 parts by mass, relative to 100 parts by mass of the total of the pre-reaction product (A), the benzoxazine compound (B), and the reactive compound (C).

[0107] The content of the benzoxazine compound (B) is not particularly limited, but is preferably 1 to 40 parts by mass, more preferably 3 to 30 parts by mass, and even more preferably 3 to 20 parts by mass, relative to 100 parts by mass of the total of the preliminary reaction product (A), the benzoxazine compound (B) and the reactive compound (C).

[0108] The content of the reactive compound (C) is not particularly limited, but is preferably 20 to 98 parts by mass, more preferably 30 to 94 parts by mass, and even more preferably 50 to 92 parts by mass, relative to 100 parts by mass of the total of the pre-reaction product (A), the benzoxazine compound (B), and the reactive compound (C). When the reactive compound (C) contains a maleimide compound (when the reactive compound (C) is a maleimide compound), the content of the maleimide compound is preferably 30 to 70 parts by mass, more preferably 30 to 60 parts by mass, and even more preferably 40 to 60 parts by mass, relative to 100 parts by mass of the total of the pre-reaction product (A), the benzoxazine compound (B), and the reactive compound (C).

[0109] If the pre-reaction product (A) is too little, that is, the sum of the benzoxazine compound (B) and the reactive compound (C) is too much, there is a tendency that the relative dielectric constant becomes high, it is difficult to maintain excellent low dielectric properties, or it is difficult to remove smear. In addition, if the pre-reaction product (A) is too much, that is, the sum of the benzoxazine compound (B) and the reactive compound (C) is too little, there is a tendency that it is easy to remove smear too much. That is, if the benzoxazine compound (B) is too little, or the reactive compound (C) is too little, there is a tendency that it is easy to remove smear too much. In addition, if the benzoxazine compound (B) is too much, or the sum with the reactive compound (C) is too much, there is a tendency that it is difficult to maintain excellent low dielectric properties, or it is difficult to remove smear. Therefore, when the contents of the preliminary reaction product (A), the benzoxazine compound (B), and the reactive compound (C) are within the above ranges, the ease of desmearing and the like can be well adjusted while maintaining excellent low dielectric properties.

[0110] (Inorganic filler)

[0111] The resin composition may or may not contain an inorganic filler, but preferably contains an inorganic filler. The inorganic filler is not particularly limited as long as it can be used as an inorganic filler contained in the resin composition. As the inorganic filler, 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 can be cited. Among them, silicon dioxide, metal hydroxides such as magnesium hydroxide and aluminum hydroxide, aluminum oxide, boron nitride, and barium titanate 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.

[0112] The inorganic filler may be a surface-treated inorganic filler or an untreated inorganic filler. Examples of the surface treatment include treatment with a silane coupling agent.

[0113] 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.

[0114] Regarding the silane coupling agent, as a silane coupling agent having a vinyl group, for example, vinyl triethoxysilane and vinyl trimethoxysilane can be listed. 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 listed. 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 diethoxysilane, and 3-methacryloyloxypropyl ethyl diethoxysilane can be listed. 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 listed. 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.

[0115] The average particle size of the inorganic filler 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.

[0116] As described above, the resin composition may contain an inorganic filler. When the resin composition contains the inorganic filler, the content of the inorganic filler is preferably 10 to 250 parts by mass, more preferably 40 to 200 parts by mass, relative to 100 parts by mass of the total mass of the pre-reaction product (A), the benzoxazine compound (B) and the reactive compound (C).

[0117] (Other ingredients)

[0118] The resin composition involved in the present embodiment may also contain components (other components) other than the pre-reaction product (A), the benzoxazine compound (B) and the reactive compound (C) as needed 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, it not only contains the inorganic filler as described above, but also may contain additives such as reactive compounds other than the reactive compound (C), 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.

[0119] The resin composition involved in this embodiment may also contain reactive compounds (other reactive compounds) other than the reactive compound (C). The other reactive compound is a compound different from the benzoxazine compound (B) and the reactive compound (C), that is, a reactive compound that does not have an unsaturated double bond in the molecule. The other reactive compound is not particularly limited, and examples thereof include benzoxazine compounds (D) other than the benzoxazine compound (B), acenaphthylene compounds, cyanate compounds, and active ester compounds. The other reactive compounds may be used alone or in combination of two or more.

[0120] The benzoxazine compound (D) is a compound different from the benzoxazine compound (B) and the reactive compound (C). That is, the benzoxazine compound (D) is a benzoxazine compound that does not have an unsaturated double bond such as an alkenyl group in the molecule, and is a compound having a benzoxazine ring in the molecule, and examples thereof include benzoxazine resins, etc. Examples of the benzoxazine compound include, for example, a benzoxazine compound having a phenolphthalein structure in the molecule (phenolphthalein type benzoxazine compound), a bisphenol F type benzoxazine compound, and a diaminodiphenylmethane (DDM) type benzoxazine compound. More specifically, the benzoxazine compound includes 3,3′-(methylene-1,4-diphenylene)bis(3,4-dihydro-2H-1,3-benzoxazine) (Pd-type benzoxazine compound), 2,2-bis(3,4-dihydro-2H-3-phenyl-1,3-benzoxazine)methane (Fa-type benzoxazine compound), and the like.

[0121] 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.

[0122] 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.

[0123] 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.

[0124] 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-butylperoxym-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-butylperoxym-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.

[0125] 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 cycloalkane 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.

[0126] As described above, the resin composition involved in the present embodiment may contain a silane coupling agent. The silane coupling agent may be contained in the resin composition, or may be contained in the form of a silane coupling agent that has been pre-surface treated for the inorganic filler contained in the resin composition. Wherein, as the silane coupling agent, it is preferably contained in the form of a silane coupling agent that has been pre-surface treated for the inorganic filler, and more preferably, it is contained in the form of a silane coupling agent that has been pre-surface treated for the inorganic filler, and the resin composition also contains a silane coupling agent. In addition, with respect to prepreg, it may be contained in the form of a silane coupling agent that has been pre-surface treated for a fibrous substrate 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 surface treated as described above may be cited.

[0127] 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, each of the exemplified flame retardants can be used alone, or two or more can be used in combination.

[0128] (use)

[0129] 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.

[0130] (Manufacturing method)

[0131] The method for producing the resin composition is not particularly limited, and examples thereof include a method in which, after performing a preliminary reaction for obtaining the preliminary reaction product (A), the preliminary reaction product (A), the benzoxazine compound (B) and the reactive compound (C) are mixed under conditions such that the contents thereof are in a predetermined amount, etc. In addition, in the case of obtaining a varnish-like composition containing an organic solvent, the method described below, etc. may be used.

[0132] By using the resin composition according to the present embodiment, a prepreg, a metal foil-clad laminate, a wiring board, a metal foil with a resin, and a film with a resin can be obtained as described below.

[0133] [Prepreg]

[0134] Figure 1 This is a schematic cross-sectional view showing an example of the prepreg 1 according to the embodiment of the present invention.

[0135] 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.

[0136] 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.

[0137] 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.

[0138] 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.

[0139] 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 is added as needed, 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 modulating a varnish-like resin composition. As the organic solvent used herein, as long as it is an organic solvent that can dissolve the pre-reaction product (A), the benzoxazine 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) and the like can be cited.

[0140] 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.

[0141] 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.

[0142] 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.

[0143] 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.

[0144] The resin composition involved in the present embodiment is a resin composition that can obtain a cured product having low dielectric properties, heat resistance, excellent adhesion to metal foil and desmearing property and a high glass transition temperature. Therefore, the prepreg having the semi-cured product of the resin composition or the resin composition is a prepreg that can obtain a cured product having low dielectric properties, heat resistance, excellent adhesion to metal foil and desmearing property and a high glass transition temperature. Moreover, the prepreg can well manufacture a wiring board having an insulating layer of a cured product having low dielectric properties, heat resistance, excellent adhesion to metal foil and desmearing property and a high glass transition temperature.

[0145] [Gold foil laminate]

[0146] 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.

[0147] 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 1An insulating layer 12 of a cured product of the prepreg 1 shown; and a metal foil-clad laminate of a metal foil 13 stacked together with 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.

[0148] 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.

[0149] The resin combination that the present embodiment is related to is the resin combination that can obtain the solidified product with low dielectric properties, heat resistance, excellent adhesion and desmear property with metal foil and the high glass transition temperature.Therefore, the metal foil clad laminated board having the insulating layer of the solidified product comprising the resin combination is the metal foil clad laminated board having the insulating layer of the solidified product comprising low dielectric properties, heat resistance, excellent adhesion and desmear property with metal foil and the high glass transition temperature.And, the metal foil clad laminated board can well manufacture the wiring board having the insulating layer of the solidified product comprising low dielectric properties, heat resistance, excellent adhesion and desmear property with metal foil and the high glass transition temperature.

[0150] [Wiring board]

[0151] Figure 3It is a schematic cross-sectional view showing an example of wiring board 21 according to the embodiment of the present invention.

[0152] like Figure 3 As 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 the insulating layer 12. Examples of the wiring board 21 include: Figure 1 The insulating layer 12 used by curing the prepreg 1 shown in the figure; and a wiring board etc. which is laminated together with the insulating layer 12 and forms wiring 14 by removing a part of the metal foil 13. In addition, the insulating layer 12 may be formed of a cured product of the resin composition or a cured product of the prepreg.

[0153] 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: Semi Additive Process) or a modified semi-additive process (MSAP: Modified Semi Additive Process) can be cited.

[0154] The wiring board 21 is a wiring board including an insulating layer 12 including a cured product having low dielectric properties, heat resistance, excellent adhesion to metal foil and desmear properties, and a high glass transition temperature.

[0155] [Metal foil with resin]

[0156] Figure 4 It is a schematic cross-sectional view showing an example of the metal foil with resin 31 according to the present embodiment.

[0157] like Figure 4As 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.

[0158] 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.

[0159] As the metal foil, the metal foil used in the metal foil laminate and the metal foil with resin can be used without limitation. As the metal foil, for example, copper foil and aluminum foil can be cited.

[0160] 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.

[0161] 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.

[0162] The resin composition that the present embodiment is related to is a resin composition that can obtain a solidified product with low dielectric properties, heat resistance, excellent adhesion and desmearing property with 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 solidified product with low dielectric properties, heat resistance, excellent adhesion and desmearing property with 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 solidified product comprising low dielectric properties, heat resistance, excellent adhesion and desmearing property with 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 a wiring board obtained by using the metal foil with resin, a wiring board with an insulating layer of a solidified product comprising low dielectric properties, heat resistance, excellent adhesion and desmearing property with metal foil and a high glass transition temperature can be obtained.

[0163] [Film with resin]

[0164] Figure 5 It is a schematic cross-sectional view showing an example of the film 41 with resin according to the present embodiment.

[0165] 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.

[0166] 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.

[0167] 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.

[0168] 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.

[0169] 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.

[0170] 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.

[0171] The resin composition involved in the present embodiment is a resin composition that can obtain a solidified product with low dielectric properties, heat resistance, excellent adhesion to metal foil and desmearing property 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 solidified product with low dielectric properties, heat resistance, excellent adhesion to metal foil and desmearing property and a high glass transition temperature. And, the film with resin can be used when the wiring board with the insulating layer of the solidified product with low dielectric properties, heat resistance, excellent adhesion to metal foil and desmearing property and a high glass transition temperature is manufactured. For example, a multilayer wiring board can be manufactured by peeling off the supporting film after being stacked on the wiring board, or, after peeling off the supporting film, being stacked on the wiring board. As the wiring board obtained by using the film with resin, a wiring board with the insulating layer of the solidified product with low dielectric properties, heat resistance, excellent adhesion to metal foil and desmearing property and a high glass transition temperature can be obtained.

[0172] As described above, this specification discloses the technologies of various embodiments, and its main technologies are summarized as follows.

[0173] The first technical solution relates to a resin composition, which contains: a pre-reaction product (A) obtained by pre-reacting a mixture of a polyphenylene ether compound (a1) having a hydroxyl group in the molecule and an acid anhydride (a2) having an acid anhydride group in the molecule; a benzoxazine compound (B) having an alkenyl group in the molecule; and a reactive compound (C) having an unsaturated double bond in the molecule.

[0174] The resin composition according to the second invention is the resin composition according to the first invention, wherein the equivalent ratio of the acid anhydride group of the acid anhydride (a2) to the hydroxyl group of the polyphenylene ether compound (a1) is 1.5 or less.

[0175] The resin composition according to the third invention is the resin composition according to the first or second invention, wherein the content of the preliminary reaction product (A) is 1 to 40 parts by mass relative to 100 parts by mass of the total of the preliminary reaction product (A), the benzoxazine compound (B) and the reactive compound (C).

[0176] The resin composition according to the fourth aspect is the resin composition according to any one of the first to third aspects, wherein the content of the benzoxazine compound (B) is 1 to 40 parts by mass based on 100 parts by mass of the total of the preliminary reaction product (A), the benzoxazine compound (B) and the reactive compound (C).

[0177] The resin composition according to the fifth technical solution is the resin composition according to any one of the first to fourth technical solutions, wherein the content of the reactive compound (C) is 20 to 98 parts by mass relative to 100 parts by mass of the total of the preliminary reaction product (A), the benzoxazine compound (B) and the reactive compound (C).

[0178] The resin composition according to the sixth invention is the resin composition according to any one of the first to fifth inventions, wherein the acid anhydride (a2) contains an acid anhydride having one or more cyclic acid anhydride groups in the molecule.

[0179] The resin composition according to a seventh aspect is the resin composition according to any one of the first to sixth aspects, wherein the preliminary reaction product (A) includes a preliminary reaction product obtained by previously reacting the polyphenylene ether compound (a1) and the acid anhydride (a2).

[0180] The resin composition according to the eighth invention is the resin composition according to any one of the first to seventh inventions, wherein the preliminary reaction product (A) contains an ester and a carboxyl-modified polyphenylene ether compound whose terminal is modified with a substituent having one or more ester bonds and one or more carboxyl groups.

[0181] The resin composition involved in the 9th technical solution is the resin composition involved in any one of the 1st to 8th technical solutions, wherein the reactive compound (C) contains at least one selected from the group consisting of an unsaturated double bond-modified polyphenylene ether compound whose terminal is modified with a substituent having an unsaturated double bond, an allyl compound, an acrylate compound, a methacrylate compound, a polybutadiene compound, a styrene compound and a maleimide compound.

[0182] The resin composition involved in the tenth technical solution is the resin composition involved in any one of the first to ninth technical solutions, wherein the reactive compound (C) contains at least one selected from the group consisting of an unsaturated double bond-modified polyphenylene ether compound whose terminal is modified with a substituent having an unsaturated double bond and a maleimide compound.

[0183] The resin composition involved in the 11th technical solution is the resin composition involved in any one of the 1st to 10th technical solutions, wherein the reactive compound (C) contains a maleimide compound, and the content of the maleimide compound is 30 to 70 parts by mass relative to 100 parts by mass of the total of the pre-reaction product (A), the benzoxazine compound (B) and the reactive compound (C).

[0184] The resin composition according to the twelfth invention is the resin composition according to any one of the first to eleventh inventions, further comprising an inorganic filler.

[0185] The resin composition according to the 13th invention is the resin composition according to the 12th invention, wherein the inorganic filler is surface-treated with a silane coupling agent.

[0186] A fourteenth technical solution is directed to a prepreg comprising: the resin composition according to any one of the first to thirteenth technical solutions or a semi-cured product of the resin composition; and a fibrous base material.

[0187] A fifteenth invention relates to a film with a resin, comprising: a resin layer comprising the resin composition according to any one of the first to thirteenth inventions or a semi-cured product of the resin composition; and a support film.

[0188] A sixteenth invention relates to a metal foil with resin, comprising: a resin layer containing the resin composition according to any one of the first to thirteenth inventions or a semi-cured product of the resin composition; and a metal foil.

[0189] A seventeenth invention relates to a metal-clad laminate comprising: an insulating layer comprising a cured product of the resin composition according to any one of the first to thirteenth inventions; and a metal foil.

[0190] An eighteenth invention relates to a metal foil-clad laminate comprising: an insulating layer formed from a cured product of the prepreg according to the fourteenth invention; and a metal foil.

[0191] A nineteenth invention relates to a wiring board comprising: an insulating layer formed of a cured product of the resin composition according to any one of the first to thirteenth inventions; and wiring.

[0192] The twentieth technical solution is directed to a wiring board comprising: an insulating layer formed of a cured product of the prepreg according to the fourteenth technical solution; and wiring.

[0193] According to the present invention, a resin composition having excellent low dielectric properties, heat resistance, adhesion to metal foil and desmearing properties 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.

[0194] 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.

[0195] Example

[0196] [Preliminary reaction product (A): Preliminary reaction products A1 to A9]

[0197] First, a preliminary reaction product (A) used in each of the Examples and Comparative Examples was prepared.

[0198] The components used in producing the preliminary reaction product (A) will be described.

[0199] (Polyphenylene ether compound (a1))

[0200] 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)

[0201] (anhydride (a2))

[0202] Acid anhydride 1: a mixture of 4-methylhexahydrophthalic anhydride and hexahydrophthalic anhydride (mass ratio 70:30) (RIKACID MH-700 manufactured by Shin Nippon Rika Co., Ltd., monofunctional acid anhydride, liquid alicyclic acid anhydride, functional group equivalent of anhydride group 161 to 166 g / eq, freezing point 20°C)

[0203] Acid anhydride 2: octenyl succinic anhydride (RIKACID OSA manufactured by Shin Nippon Chemical Co., Ltd., monofunctional acid anhydride, liquid alicyclic acid anhydride, functional group equivalent of acid anhydride group 205-220 g / eq, freezing point below 15°C)

[0204] (Preparation method)

[0205] First, a polyphenylene ether compound (a1) and an acid anhydride (a2) are mixed in the composition (parts by mass) described in Table 1, and diluted with toluene so that the solid content concentration becomes 40% by mass. A disperser is used to stir and mix. Through this operation, the polyphenylene ether compound (a1) and the acid anhydride (a2) react to obtain a pre-reaction product. The reaction conditions of the polyphenylene ether compound (a1) and the acid anhydride (a2) are as follows: the temperature (reaction temperature) and the stirring and mixing time (reaction time) when stirring and mixing using a disperser are adjusted so that the ring-opening rate obtained by the above-mentioned calculation method is as high as possible. Specifically, the reaction temperature is set to 30°C and the reaction time is set to 5 hours. In addition, the ring-opening rates of the pre-reaction products A1 to A9 are shown in Table 1.

[0206] It should be noted that the equivalent ratios recorded in Table 1 are obtained based on the functional groups (reactive groups) of the reaction. That is, the equivalent ratios recorded in Table 1 are obtained by dividing each mixed amount by the equivalent of each functional group. It should be noted that the equivalent ratio is not calculated as an integer ratio, but a ratio obtained by rounding off or the like to properly approximate the value. That is, the equivalent ratios recorded in Table 1 are the ratios approximated by rounding off the ratio of the values ​​obtained by dividing each mixed amount by the equivalent of each functional group.

[0207] Specifically, the pre-reaction product A1 is described. The phenol equivalent (hydroxyl equivalent) of the polyphenylene ether compound (a1) is 850 g / eq, and the functional group equivalent of the anhydride group of the anhydride (a2) is 161 to 166 g / eq. It should be noted that the functional group equivalent of the anhydride group of the anhydride (a2) is assumed to be 163 g / eq for calculation. The mixing amount of the polyphenylene ether compound (a1) is 2.5 parts by mass, and the mixing amount of the anhydride (a2) is 0.5 parts by mass. Based on these data, it can be calculated that the equivalent ratio (hydroxyl equivalent of the polyphenylene ether compound (a1) : anhydride group equivalent of the anhydride (a2)) is (2.5 / 850): (0.5 / 163) = about 1:1. Therefore, the equivalent ratio in the pre-reaction product A1 is 1:1. That is, the equivalent ratio of the anhydride group of the acid anhydride (a2) to the hydroxyl group of the polyphenylene ether compound (a1) is 1.

[0208] Table 1

[0209]

[0210] [Examples 1 to 15 and Comparative Examples 1 to 6]

[0211] The components used to prepare the prepreg in this example are described below.

[0212] (Pre-reaction product (A))

[0213] As the preliminary reaction product (A), the preliminary reaction products A1 to A9 described above were used. In addition, the composition (mass parts) of the preliminary reaction product (A) in Table 2 and Table 3 represents the mass of the solid content.

[0214] (PPE)

[0215] PPE: The same PPE as that used in preparing the pre-reaction product was used. Specifically, 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) was used. It should be noted that the examples using this PPE (in Table 2, the examples with the composition of PPE recorded: Comparative Example 1 and Comparative Example 2) did not carry out the above-mentioned pre-reaction.

[0216] (anhydride)

[0217] Acid anhydride 1: The same acid anhydride as that used in preparing the pre-reaction product was used. Specifically, a mixture of 4-methylhexahydrophthalic anhydride and hexahydrophthalic anhydride (mass ratio 70:30) was used (RIKACID MH-700 manufactured by Shin Nippon Rika Co., Ltd., monofunctional acid anhydride, liquid alicyclic acid anhydride, functional group equivalent of anhydride group 161 to 166 g / eq, freezing point 20°C). It should be noted that the example using this acid anhydride 1 (in Table 2, the example with the composition of acid anhydride 1 recorded: Comparative Example 2) did not carry out the above-mentioned pre-reaction.

[0218] In addition, in Comparative Example 3, the above-mentioned preliminary reaction was not performed.

[0219] (Benzoxazine compounds)

[0220] Alkenyl-containing benzoxazine compound (B): a benzoxazine compound having an allyl group as an alkenyl group in the molecule (represented by the above formula (11) and X is a methylene group, R 41 and R 42 A benzoxazine compound in which q and r are 1 and ALPd manufactured by Shikoku Chemical Industry Co., Ltd., with a functional group equivalent of benzoxazine group of 244 g / eq)

[0221] Alkenyl-free benzoxazine compound 1: a benzoxazine compound having no alkenyl group in the molecule (3,3'-(methylene-1,4-diphenylene)bis(3,4-dihydro-2H-1,3-benzoxazine, a Pd-type benzoxazine compound manufactured by Shikoku Chemicals Co., Ltd., functional group equivalent of benzoxazine group 217 g / eq)

[0222] Alkenyl-free benzoxazine compound 2: a benzoxazine compound having no alkenyl group in the molecule (2,2-bis(3,4-dihydro-2H-3-phenyl-1,3-benzoxazine)methane, a Fa-type benzoxazine compound manufactured by Shikoku Chemical Industry Co., Ltd., a functional group equivalent of benzoxazine group 210 g / eq)

[0223] (Reactive compound (C))

[0224] (Reactive compound: maleimide compound)

[0225] 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)

[0226] 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)

[0227] (Reactive compound: reactive compound other than maleimide compound)

[0228] Modified PPE1: 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)

[0229] Modified PPE2: a polyphenylene ether compound having a methacryloyl group at a molecular terminal (methacryloyl-modified polyphenylene ether) (SA9000 manufactured by Saudi Basic Industries Corporation, weight average molecular weight Mw 1700, functional group equivalent of methacryloyl group 850 g / eq)

[0230] (Curing accelerator)

[0231] 2E4MZ: Imidazole curing accelerator (2-ethyl-4-methylimidazole, 2E4MZ manufactured by Shikoku Chemical Industry Co., Ltd.)

[0232] (Inorganic filler)

[0233] Inorganic filler 1: Spherical silica surface-treated with vinyl silane (SC2300-SVJ manufactured by Admatechs Company Limited)

[0234] Inorganic filler 2: Spherical silica surface-treated with phenylaminosilane (SC2500-SXJ manufactured by Yaduma Co., Ltd.)

[0235] (Preparation method)

[0236] First, the components other than the inorganic filler are added to methyl ethyl ketone (MEK) in a manner such that the solid content concentration becomes 60% by mass according to the composition (mass parts) recorded in Table 2 and Table 3, and a dispersion machine is used to stir and mix to make it uniform. The inorganic filler is added to the uniform mixture according to the composition (mass parts) recorded in Table 2 and Table 3, and a dispersion machine is used to stir and mix for 2 hours to make it uniform. By doing so, a varnish-like resin composition (varnish) is obtained.

[0237] Next, prepregs and evaluation substrates 1 to 3 (metal foil-clad laminates) were obtained as follows.

[0238] 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.

[0239] Next, an evaluation substrate 1 (metal foil-clad laminate) was obtained in the following manner.

[0240] 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.

[0241] 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).

[0242] 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).

[0243] Evaluation substrates 1 to 3 (copper-clad laminates) prepared as described above were evaluated by the methods shown below.

[0244] [Desmearing property]

[0245] 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.

[0246] 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 , it is evaluated as "B(O)", if it is 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 (×)".

[0247] 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(O)" 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.

[0248] [Relative dielectric constant Dk]

[0249] 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.

[0250] [Glass transition temperature Tg]

[0251] 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.

[0252] [Heat resistance (oven resistance)]

[0253] The evaluation substrate 3 was placed in a dryer set at 240°C, 260°C and 280°C for 1 hour. Then, the laminate was visually observed to see if it expanded after being placed. If it was placed in a dryer at 240°C, it was evaluated as "A(×)". In addition, if it was placed in a dryer at 260°C, it was confirmed that it expanded, but even if it was placed in a dryer at 240°C, it was not confirmed that it expanded, and it was evaluated as "B(Δ)". In addition, if it was placed in a dryer at 280°C, it was confirmed that it expanded, but even if it was placed in a dryer at 260°C, it was not confirmed that it expanded, and it was evaluated as "C(O)". In addition, even if it was placed in a dryer at 280°C, it was not confirmed that it expanded, and it was evaluated as "D(◎)". It should be noted that "B(Δ)", "C(○)" and "D(◎)" are judged to have good oven heat resistance, preferably "C(O)" and "D(◎)", and more preferably "D(◎)".

[0254] [Peel strength]

[0255] The copper foil was peeled off from the evaluation substrate 3 (metal foil-clad laminate), 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 at a speed of 50 mm / min using a tensile tester, and the peel strength (N / mm) at that time was measured.

[0256] The results of the above evaluations are shown in Tables 2 and 3.

[0257] Table 2

[0258]

[0259] Table 3

[0260]

[0261] It can be seen from Tables 2 and 3 that when the resin composition contains a pre-reaction product (A) obtained by pre-reacting the polyphenylene ether compound (a1) and the acid anhydride (a2), the benzoxazine compound (B) and the reactive compound (C) (Examples 1 to 15), a cured product having low dielectric properties, heat resistance, excellent adhesion to metal foil and desmear properties and a high glass transition temperature is obtained.

[0262] In contrast, it is known that when containing PPE that has not been pre-reacted but not containing the pre-reaction product (A) (Comparative Example 1 and Comparative Example 2), the glass transition temperature is low, and the desmearing property is poor, and the peel strength is also poor. It is known that in Comparative Example 1, since it not only does not contain the pre-reaction product, but also does not contain anhydride, the resin is easily eliminated too much by desmearing. In addition, in Comparative Example 2, although it does not contain the pre-reaction product, it contains PPE and anhydride that have not been pre-reacted, and the result is that the dielectric loss factor and heat resistance are also poor. In addition, it is known that when not containing the pre-reaction product (A) and not containing PPE and anhydride that have not been pre-reacted (Comparative Example 3), it is difficult to desmear. It can also be seen from these that it is necessary to contain the pre-reaction product (A).

[0263] In addition, it is known that when the benzoxazine compound (B) is not contained (Comparative Examples 4 to 6), the glass transition temperature is low and the peel strength is also poor. In addition, it is known that even when the benzoxazine compound (B) is not contained but a benzoxazine compound other than the benzoxazine compound (B) is contained (Comparative Examples 4 and 5), the glass transition temperature is low and the peel strength is also poor.

[0264] When the pre-reaction product (A) contains a pre-reaction product (A1 to A8) obtained by pre-reacting in such a way that the equivalent ratio of the acid anhydride group of the acid anhydride (a2) to the hydroxyl group of the polyphenylene ether compound (a1) becomes 1.5 or less (Examples 1 to 8 and Examples 10 to 15), the heat resistance is higher than when the pre-reaction product (A9) obtained by pre-reacting in such a way that the equivalent ratio exceeds 1.5 (Example 9). It can be seen from this that by using the pre-reaction product obtained by pre-reacting in such a way that the equivalent ratio becomes 1.5 or less, a cured product with low dielectric properties, excellent adhesion to metal foil and desmearing properties, high glass transition temperature and more excellent heat resistance can be obtained.

[0265] This application is based on Japanese patent application No. 2022-115730 filed on July 20, 2022, and the contents are incorporated herein by reference.

[0266] In order to describe the present invention, the present invention has been appropriately and fully described above through the embodiments, but it should be recognized that those skilled in the art can easily change and / or improve the above embodiments. Therefore, the changed embodiments or improved embodiments implemented by those skilled in the art, as long as they do not deviate from the protection scope of the claims recorded in the claims, the changed embodiments or the improved embodiments can be interpreted as being included in the protection scope of the claims.

[0267] Industrial Applicability

[0268] According to the present invention, a resin composition having low dielectric properties, heat resistance, adhesion to metal foil and excellent desmearing properties 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.

Claims

1. A resin composition, characterized in that contain: A pre-reaction product (A) obtained by reacting in advance a mixture of a polyphenylene ether compound (a1) having a hydroxyl group in the molecule and an acid anhydride (a2) having an acid anhydride group in the molecule; a benzoxazine compound (B) having an alkenyl group in the molecule; and A reactive compound (C) having an unsaturated double bond in the molecule.

2. The resin composition according to claim 1, characterized in that The equivalent ratio of the anhydride group of the acid anhydride (a2) to the hydroxyl group of the polyphenylene ether compound (a1) is 1.5 or less.

3. The resin composition according to claim 1, characterized in that The content of the preliminary reaction product (A) is 1 to 40 parts by mass based on 100 parts by mass of the total of the preliminary reaction product (A), the benzoxazine compound (B) and the reactive compound (C).

4. The resin composition according to claim 1, characterized in that The content of the benzoxazine compound (B) is 1 to 40 parts by mass based on 100 parts by mass of the total of the preliminary reaction product (A), the benzoxazine 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 20 to 98 parts by mass based on 100 parts by mass of the total of the preliminary reaction product (A), the benzoxazine compound (B) and the reactive compound (C).

6. The resin composition according to claim 1, characterized in that The acid anhydride (a2) includes an acid anhydride having one or more cyclic acid anhydride groups in the molecule.

7. The resin composition according to claim 1, characterized in that The preliminary reaction product (A) includes a preliminary reaction product obtained by allowing the polyphenylene ether compound (a1) and the acid anhydride (a2) to react in advance.

8. The resin composition according to claim 1, characterized in that The preliminary reaction product (A) contains an ester and a carboxyl-modified polyphenylene ether compound whose terminal is modified with a substituent having one or more ester bonds and one or more carboxyl groups.

9. The resin composition according to claim 1, characterized in that The reactive compound (C) contains at least one selected from the group consisting of an unsaturated double bond-modified polyphenylene ether compound whose terminal is modified with a substituent having an unsaturated double bond, an allyl compound, an acrylate compound, a methacrylate compound, a polybutadiene compound, a styrene compound, and a maleimide compound.

10. The resin composition according to claim 1, characterized in that The reactive compound (C) contains at least one selected from the group consisting of an unsaturated double bond-modified polyphenylene ether compound whose terminal is modified with a substituent having an unsaturated double bond and a maleimide compound.

11. The resin composition according to claim 1, characterized in that The reactive compound (C) contains a maleimide compound, The content of the maleimide compound is 30 to 70 parts by mass based on 100 parts by mass of the total of the preliminary reaction product (A), the benzoxazine compound (B), and the reactive compound (C).

12. The resin composition according to claim 1, characterized in that Also contains: Inorganic filler materials.

13. The resin composition according to claim 12, characterized in that The inorganic filler is surface treated with a silane coupling agent.

14. A prepreg, characterized in that include: The resin composition according to any one of claims 1 to 13 or a semi-cured product of the resin composition; as well as Cellulosic substrate.

15. A film with resin, characterized in that include: A resin layer comprising the resin composition according to any one of claims 1 to 13 or a semi-cured product of the resin composition; as well as Support membrane.

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

17. 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 13; as well as Metal foil.

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

19. 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 13; as well as wiring.

20. A wiring board, characterized in that include: An insulating layer comprising a cured product of the prepreg according to claim 14; as well as wiring.

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