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

Abstract

One aspect of the present invention relates to a resin composition containing: a polyphenylene ether compound (A); a reactive compound (B) having an unsaturated double bond in the molecule; and at least one additive (C) selected from the group consisting of a heavy metal deactivator (C1) having a phenolic hydroxyl group and at least one of an amino group and a triazole structure in the molecule, a phosphite antioxidant (C2), and a hindered phenol antioxidant (C3). The phosphite ester antioxidant (C2) has a tertiary butyl and phosphite ester structure in a molecule, and the hindered phenol antioxidant (C3) has a tertiary butyl and a phenolic hydroxyl group in a 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] The substrate material used for forming the insulating layer of the wiring board is required to have not only low dielectric properties but also excellent adhesion to metal foil and interlayer adhesion, and to obtain a cured product in which the decrease in interlayer adhesion due to heating and moisture absorption is sufficiently suppressed.

[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 having low dielectric properties, excellent adhesion to metal foil and interlayer adhesion, and fully suppressing the decrease in interlayer adhesion caused by heating and moisture absorption. 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, which contains: a polyphenylene ether compound (A); a reactive compound (B) having an unsaturated double bond in the molecule; and at least one additive (C) selected from the group consisting of a heavy metal deactivator (C1), a phosphite antioxidant (C2) and a hindered phenol antioxidant (C3), wherein the heavy metal deactivator (C1) has at least one of an amino group and a triazole structure, and a phenolic hydroxyl group in the molecule, the phosphite antioxidant (C2) has a tert-butyl group and a phosphite structure in the molecule, and the hindered phenol antioxidant (C3) has a tert-butyl group and a phenolic hydroxyl group 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 diversification, high performance, thinness and miniaturization. Along with this, the wiring boards used in these products are also further required to have finer conductor wiring, multilayered conductor wiring layers, thinning and high performance of 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 a finer wiring. 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. In addition, as mentioned above, the wiring board is required to be multilayered, and when the insulating layer is formed by multiple layers, it is also required to have high interlayer adhesion to prevent interlayer peeling between the insulating layers. Therefore, it is required that the substrate material used to constitute the insulating layer of the wiring board can obtain the adhesion between adjacent cured products, that is, a cured product with excellent interlayer adhesion.

[0019] The wiring boards used in various electronic devices are also required to be less susceptible to the influence of external environmental changes. For example, the wiring boards are also required to have excellent interlayer adhesion and not to peel off the layers in environments with high humidity and high temperature, so that the wiring boards can be used in environments with high humidity and high temperature. Therefore, the substrate material used to form the insulating layer of the wiring board is required to be able to obtain a cured product that maintains excellent interlayer adhesion even when it absorbs moisture and is heated.

[0020] The present inventors have conducted various studies and found that the above-mentioned object can be achieved by the following present invention, that is, providing a resin composition that can obtain a cured product with low dielectric properties, excellent adhesion to metal foil and interlayer adhesion, and fully suppresses the decrease in interlayer adhesion caused by heating and moisture absorption.

[0021] As described above, the wiring board is required to have excellent interlayer adhesion, and it is also required to maintain the excellent interlayer adhesion even if it is affected by changes in the external environment. According to the research of the present inventors, it was found that when a resin composition containing polyphenylene ether is used as a substrate material for constituting an insulating layer of a wiring board, the interlayer adhesion is sometimes insufficient based on its composition. The present inventors found that, for example, in a wiring board obtained by using a resin composition containing a reaction product of polyphenylene ether and an unsaturated carboxylic acid or anhydride as a polyphenylene ether component as described in Patent Document 1, the interlayer adhesion is sometimes insufficient. It is believed that the reaction product has a carboxyl group in the molecule. It is believed that the reaction product having a carboxyl group in the molecule acts on a metal foil in contact with an insulating layer containing a cured product of the resin composition, so that the components constituting the metal foil are dissolved into the insulating layer. It is believed that, for example, when the metal foil is a copper foil treated with chromate, the reaction product acts on the metal foil, and the chromium component is dissolved from the metal foil into the insulating layer. It is also believed that when a metal foil is removed from a metal foil-clad laminate and an insulating layer is further formed thereon during the manufacture of a wiring board, the eluted component remains in the insulating layer of the portion where the metal foil is removed, and the component reduces the interlayer adhesion. The present inventors have found that when there are not only components from the metal foil of the metal foil-clad laminate but also components that reduce the interlayer adhesion, the additive contained in the resin composition can improve the interlayer adhesion and can fully suppress the reduction of the interlayer adhesion caused by the influence of changes in the external environment. Based on the above, the following present invention has been completed.

[0022] [Resin composition]

[0023] One embodiment of the present invention relates to a resin composition, which contains: a polyphenylene ether compound (A); a reactive compound (B) having an unsaturated double bond in the molecule; and at least one additive (C) selected from the group consisting of a heavy metal deactivator (C1), a phosphite antioxidant (C2) and a hindered phenol antioxidant (C3), wherein the heavy metal deactivator (C1) has at least one of an amino group and a triazole structure and a phenolic hydroxyl group in the molecule, the phosphite antioxidant (C2) has a tert-butyl group and a phosphite structure in the molecule, and the hindered phenol antioxidant (C3) has a tert-butyl group and a phenolic hydroxyl group in the molecule. The resin composition can be cured to obtain a cured product having low dielectric properties, excellent adhesion to metal foil and interlayer adhesion, and fully suppressing the decrease in interlayer adhesion caused by heating and moisture absorption.

[0024] It is believed that the resin composition can be cured well by allowing the polyphenylene ether compound (A) to cure together with the reactive compound (B), and can obtain a cured product having excellent low dielectric properties and excellent adhesion to metal foil, which maintains the excellent low dielectric properties of the polyphenylene ether chain in the polyphenylene ether compound (A). In addition, it is believed that the resin composition can suppress the decline of interlayer adhesion even if there is a component that reduces interlayer adhesion by containing the additive (C). Therefore, it is believed that the interlayer adhesion can be improved, and the decline of interlayer adhesion caused by heating and moisture absorption can be fully suppressed. Based on these reasons, it is believed that the resin composition can obtain a cured product having low dielectric properties, excellent adhesion to metal foil and interlayer adhesion, and fully suppressing the decline of interlayer adhesion caused by heating and moisture absorption.

[0025] (Polyphenylene ether compound (A))

[0026] The polyphenylene ether compound (A) is not particularly limited as long as it has a polyphenylene ether chain in the molecule. For example, the polyphenylene ether compound (A) preferably has a repeating unit represented by the following formula (1) in the molecule.

[0027]

[0028] In formula (1), t represents 1 to 50. In addition, R1 to R4 are each independent. That is, R1 to R4 may be the same group or different groups. In addition, R1 to R4 represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkynylcarbonyl group. Among them, a hydrogen atom and an alkyl group are preferred.

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

[0030] The alkyl group is not particularly limited, 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.

[0031] 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.

[0032] The alkynyl group is not particularly limited, and is preferably an alkynyl group having 2 to 18 carbon atoms, and more preferably an alkynyl group having 2 to 10 carbon atoms. Specific examples thereof include ethynyl and prop-2-yn-1-yl (propargyl).

[0033] The alkylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted 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.

[0034] The alkenylcarbonyl group is not particularly limited as long as it is a carbonyl group substituted with an alkenyl group, and is preferably an alkenylcarbonyl group having 3 to 18 carbon atoms, and more preferably an alkenylcarbonyl group having 3 to 10 carbon atoms. Specific examples thereof include acryloyl, methacryloyl, and crotonoyl groups.

[0035] 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.

[0036] The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polyphenylene ether compound (A) are not particularly limited, and are preferably 500 to 5000, preferably 800 to 4000, and preferably 1000 to 3000. 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, for example, values ​​measured by gel permeation chromatography (GPC) can be cited. 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.

[0037] As the polyphenylene ether compound (A), for example, there can be mentioned: a polyphenylene ether compound (A1) having at least one selected from the group consisting of a hydroxyl group, a carboxyl group, an unsaturated double bond group and an ester bond in the molecule; and a pre-reaction product (A2) obtained by pre-reacting a mixture containing a polyphenylene ether compound (a2-1) and a compound (a2-2), wherein the polyphenylene ether compound (a2-1) has at least one selected from the group consisting of a hydroxyl group, a carboxyl group and an ester bond in the molecule, and the compound (a2-2) reacts with at least one of the hydroxyl group, the carboxyl group and the ester bond. The polyphenylene ether compound (A) can react with the reactive compound (B). The resin composition is cured by the reaction of the polyphenylene ether compound (A) and the reactive compound (B).

[0038] (Polyphenylene ether compound (A1))

[0039] The polyphenylene ether compound (A1) is not particularly limited as long as it is a polyphenylene ether compound having at least one selected from the group consisting of a hydroxyl group, a carboxyl group, an unsaturated double bond group and an ester bond in the molecule. As the polyphenylene ether compound (A1), for example, a polyphenylene ether compound having a hydroxyl group in the molecule (hydroxyl-containing polyphenylene ether compound) (A1-1), a polyphenylene ether compound having a carboxyl group in the molecule (carboxyl-containing polyphenylene ether compound) (A1-2), a polyphenylene ether compound having an unsaturated double bond group in the molecule (unsaturated double bond polyphenylene ether compound) (A1-3), and a polyphenylene ether compound having an ester bond in the molecule (ester bond polyphenylene ether compound) (A1-4), etc. In addition, as the polyphenylene ether compound (A1), for example, a polyphenylene ether compound having a hydroxyl group and a carboxyl group in the molecule (hydroxyl- and carboxyl-containing polyphenylene ether compound) (A1-5) and other polyphenylene ether compounds having two or more of a hydroxyl group, a carboxyl group, an unsaturated double bond group and an ester bond in the molecule can also be cited.

[0040] (Hydroxy-containing polyphenylene ether compound (A1-1))

[0041] The hydroxyl-containing polyphenylene ether compound (A1-1) is not particularly limited as long as it is a polyphenylene ether compound having a hydroxyl group in the molecule. The hydroxyl-containing polyphenylene ether compound (A1-1) is preferably a polyphenylene ether compound having a hydroxyl group at a molecular end. As the hydroxyl-containing polyphenylene ether compound (A1-1), specifically, for example, a polyphenylene ether compound represented by the following formula (2) and a polyphenylene ether compound represented by the following formula (3) can be cited.

[0042]

[0043] In formula (2) and formula (3), R5 to R 20 and R 21 ~R36 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 36 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group or an alkynylcarbonyl group. In addition, in formula (3), Y represents a linear, branched or cyclic hydrocarbon having a carbon number of 20 or less. m and n each preferably represent 0 to 20. In addition, for m and n, the total value of m and n is preferably represented by a numerical value of 1 to 30. Therefore, it is more preferred that m represents 0 to 20, n represents 0 to 20, and the total value of m and n represents 1 to 30.

[0044] 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).

[0045]

[0046] 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.

[0047] 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.

[0048]

[0049] 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).

[0050] (Carboxyl group-containing polyphenylene ether compound (A1-2) and hydroxyl group- and carboxyl group-containing polyphenylene ether compound (A1-5))

[0051] The carboxyl-containing polyphenylene ether compound (A1-2) is not particularly limited as long as it is a polyphenylene ether compound having a carboxyl group in the molecule. The carboxyl-containing polyphenylene ether compound (A1-2) is preferably a polyphenylene ether compound having a carboxyl group at the molecular end. In addition, the hydroxyl- and carboxyl-containing polyphenylene ether compound (A1-5) is not particularly limited as long as it is a polyphenylene ether compound having a carboxyl group and a hydroxyl group in the molecule. The hydroxyl- and carboxyl-containing polyphenylene ether compound (A1-5) is preferably a polyphenylene ether compound having a carboxyl group and a hydroxyl group at the molecular end, respectively. As the carboxyl-containing polyphenylene ether compound (A1-2) and the hydroxyl- and carboxyl-containing polyphenylene ether compound (A1-5), for example, a pre-reaction product obtained by pre-reacting a mixture containing a hydroxyl-containing polyphenylene ether compound and an acid anhydride having an acid anhydride group in the molecule, as described later, etc. That is, the carboxyl-containing polyphenylene ether compound (A1-2) and the hydroxyl- and carboxyl-containing polyphenylene ether compound (A1-5) include reaction products obtained by reacting the hydroxyl-containing polyphenylene ether compound with the acid anhydride. If all hydroxyl groups of the hydroxyl-containing polyphenylene ether compound are changed into carboxyl-containing substituents by the acid anhydride, the carboxyl-containing polyphenylene ether compound (A1-2) is obtained. In addition, if part of the hydroxyl groups of the hydroxyl-containing polyphenylene ether compound are changed into carboxyl-containing substituents by the acid anhydride, the hydroxyl- and carboxyl-containing polyphenylene ether compound (A1-5) is obtained.

[0052] (Polyphenylene ether compound containing unsaturated double bond groups (A1-3))

[0053] The unsaturated double bond group-containing polyphenylene ether compound (A1-3) is not particularly limited as long as it is a polyphenylene ether compound having an unsaturated double bond group in the molecule. The unsaturated double bond group-containing polyphenylene ether compound (A1-3) may include a modified polyphenylene ether compound whose terminal is modified by a substituent having an unsaturated double bond, etc. As the unsaturated double bond-modified polyphenylene ether compound, for example, a compound in which the hydroxyl-containing polyphenylene ether compound (A1-1) is terminally modified by a substituent having an unsaturated double bond, etc., more specifically, a polyphenylene ether compound having a vinyl benzyl group (vinyl benzyl) at the molecular end (styrene-modified polyphenylene ether), a polyphenylene ether compound having an acryloyl group at the molecular end (acryloyl-modified polyphenylene ether), and a polyphenylene ether compound having a methacryloyl group at the molecular end (methacryloyl-modified polyphenylene ether), etc.

[0054] (Polyphenylene ether compound containing ester bond (A1-4))

[0055] The ester bond-containing polyphenylene ether compound (A1-4) is not particularly limited as long as it is a polyphenylene ether compound having an ester bond in the molecule.

[0056] (Preliminary reaction product (A2))

[0057] The pre-reaction product (A2) is not particularly limited as long as it is a pre-reaction product obtained by reacting a mixture containing a polyphenylene ether compound (a2-1) and a compound (a2-2) in advance, wherein the polyphenylene ether compound (a2-1) has at least one selected from the group consisting of a hydroxyl group, a carboxyl group and an ester bond in the molecule, and the compound (a2-2) reacts with at least one of the hydroxyl group, the carboxyl group and the ester bond. The compound (a2-2) is not particularly limited as long as it is a compound that reacts with at least one of the hydroxyl group, the carboxyl group and the ester bond, and examples thereof include an acid anhydride (a2-2-1) and a carbodiimide compound (a2-2-2) having an acid anhydride group in the molecule. Examples of the pre-reaction product (A2) include a pre-reaction product (A2-1) obtained by pre-reacting a mixture of a polyphenylene ether compound having a hydroxyl group in the molecule and an acid anhydride having an acid anhydride group in the molecule, and a pre-reaction product (A2-2) obtained by pre-reacting a mixture of a polyphenylene ether compound having at least one of a hydroxyl group and a carboxyl group in the molecule and a carbodiimide compound.

[0058] (Preliminary reaction product (A2-1))

[0059] The pre-reaction product (A2-1) is not particularly limited as long as it is a pre-reaction product obtained by reacting a mixture of a hydroxyl-containing polyphenylene ether compound (a2-1-1) having a hydroxyl group in the molecule and an acid anhydride (a2-2-1) having an acid anhydride group in the molecule. As the pre-reaction product (A2-1), for example, the hydroxyl-containing polyphenylene ether compound (a2-1-1) and the acid anhydride (a2-2-1) are reacted in advance, and further, it can also be a reaction product obtained by reacting in advance with other raw materials (a2-3-1), and the other raw materials (a2-3-1) are compounds that can react with at least one of the hydroxyl-containing polyphenylene ether compound (a2-1-1) and the acid anhydride (a2-2-1). It should be noted that as the hydroxyl-containing polyphenylene ether compound (a2-1-1), for example, the hydroxyl-containing polyphenylene ether compound (A1-1) and the like can be cited. If all the hydroxyl groups of the hydroxyl-containing polyphenylene ether compound (a2-1-1) are changed into carboxyl-containing substituents by the acid anhydride (a2-2-1), the compound is the carboxyl-containing polyphenylene ether compound (A1-2). In addition, if part of the hydroxyl groups of the hydroxyl-containing polyphenylene ether compound (a2-1-1) are changed into carboxyl-containing substituents by the acid anhydride (a2-2-1), the compound is the hydroxyl- and carboxyl-containing polyphenylene ether compound (A1-5).

[0060] The pre-reaction product (A2-1) may be, for example, a product obtained by reacting the hydroxy-containing polyphenylene ether compound (a2-1-1) with the acid anhydride (a2-2-1) in advance, or may be a product obtained by reacting the hydroxy-containing polyphenylene ether compound (a2-1-1) with other raw materials (a2-3-1) in advance, wherein the other raw materials (a2-3-1) are compounds that can react with at least one of the hydroxy-containing polyphenylene ether compound (a2-1-1) and the acid anhydride (a2-2-1). That is, the pre-reaction product (A2-1) may include, for example, a reaction product (A2-1-4) obtained by reacting the hydroxy-containing polyphenylene ether compound (a2-1-1) with the acid anhydride (a2-2-1), and a reaction product (A2-1-5) obtained by reacting the hydroxy-containing polyphenylene ether compound (a2-1-1), the acid anhydride (a2-2-1), and the other raw materials (a2-3-1). In addition, the mixture may be a mixture containing the hydroxy-containing polyphenylene ether compound (a2-1-1) and the acid anhydride (a2-2-1), or may be a mixture further containing the other raw materials (a2-3-1). The pre-reaction product (A2-1) may contain at least one of the reaction product (A2-1-4) and the reaction product (A2-1-5). The pre-reaction product (A2-1) may contain unreacted hydroxy-containing polyphenylene ether compound (a2-1-1), unreacted acid anhydride (a2-2-1), or unreacted other raw materials (a2-3-1). It should be noted that the other raw materials (a2-3-1) are not particularly limited as long as they are compounds that can react with at least one of the hydroxy-containing polyphenylene ether compound (a2-1-1) and the acid anhydride (a2-2-1).

[0061] The anhydride (a2-2-1) is not particularly limited as long as it is an anhydride with an anhydride group in the molecule. The anhydride group may have a structure of dehydration condensation of carboxylic acids respectively contained in different molecules, or may have a structure of dehydration condensation of 2 carboxylic acids in the molecule. In addition, the anhydride (a2-2-1) may be an anhydride (monofunctional anhydride) having 1 anhydride group in the molecule, or may be an anhydride (polyfunctional anhydride) having 2 or more anhydride groups in the molecule. The anhydride (a2-2-1) preferably contains an anhydride having 1 or more cyclic anhydride groups in the molecule. In addition, the carbon number of the anhydride (a2-2-1) is not particularly limited, and is preferably 6 or more, more preferably 8 or more, and is preferably 25 or less, more preferably 18 or less.

[0062] The acid anhydride (a2-2-1) is not particularly limited, and examples thereof include the monofunctional acid anhydride and the polyfunctional acid anhydride as described above.

[0063] 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.

[0064]

[0065] 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.

[0066] 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-furanyl) naphtho[1,2-C]furan-1,3-dione, pyromellitic anhydride, and benzophenonetetracarboxylic anhydride.

[0067] 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 methyl bicyclo [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-methyl hexahydrophthalic 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-butane tetracarboxylic 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 New 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 New Nippon Rika Co., Ltd. can be used.

[0068] The acid anhydride (a2-2-1) may be used alone or in combination of two or more.

[0069] A catalyst may also be used in the reaction of the mixture containing the hydroxyl-containing polyphenylene ether compound (a2-1-1) and the acid anhydride (a2-2-1) (the reaction of the hydroxyl-containing polyphenylene ether compound (a2-1-1) and the acid anhydride (a2-2-1)). The catalyst is not particularly limited as long as it is a catalyst that helps promote the reaction of the hydroxyl-containing polyphenylene ether compound (a2-1-1) and the acid anhydride (a2-2-1). Examples of the catalyst include 2-ethyl-4-methylimidazole (2E4MZ) and the like.

[0070] The pre-reaction product (A2-1) contains at least one of the reaction product (A2-1-4) and the reaction product (A2-1-5). In the reaction to obtain these reaction products, the hydroxyl group of the hydroxyl-containing polyphenylene ether compound (a2-1-1) acts on the anhydride group of the acid anhydride (a2-2-1), 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 (A2-1) preferably contains an ester and a carboxyl-modified polyphenylene ether compound whose terminal is modified by a substituent having an ester bond and a carboxyl group.

[0071] The reaction product is not particularly limited as long as it is at least one of the reaction product (A2-1-4) and the reaction product (A2-1-5), and examples thereof include: a compound obtained by reacting the compound represented by the formula (7) as the acid anhydride (a2-2-1) with the hydroxyl-containing polyphenylene ether compound (a2-1-1); and a compound obtained by reacting octenyl succinic anhydride as the acid anhydride (a2-2-1) with the hydroxyl-containing polyphenylene ether compound (a2-1-1). In addition, the compound obtained by reacting the compound represented by the formula (7) as the acid anhydride (a2-2-1) with the hydroxyl-containing polyphenylene ether compound (a2-1-1) varies depending on the structure of the hydroxyl-containing polyphenylene ether compound (a2-1-1), and examples thereof include a compound represented by the following formula (8).

[0072]

[0073] In formula (8), R A The following can be listed: A The same group specifically 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). Specifically, m and n each preferably represent 0 to 20.

[0074] The equivalent ratio of the anhydride group of the acid anhydride (a2-2-1) to the hydroxyl group of the hydroxyl-containing polyphenylene ether compound (a2-1-1) (anhydride group of the acid anhydride (a2-2-1) / hydroxyl group of the hydroxyl-containing polyphenylene ether compound (a2-1-1)) 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 hydroxyl groups of the hydroxyl-containing polyphenylene ether compound (a2-1-1) is 1 equivalent, the amount of the anhydride group of the acid anhydride (a2-2-1) is preferably 1.5 equivalents or less, more preferably 0.3 to 1.5 equivalents, and further preferably 0.8 to 1 equivalent. By mixing the hydroxyl-containing polyphenylene ether compound (a2-1-1) and the acid anhydride (a2-2-1) in such a manner as to fall within the equivalent ratio range, a suitable preliminary reaction product 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 hydroxyl-containing polyphenylene ether compound can also be defined as a phenol equivalent.

[0075] The conditions of the reaction are not particularly limited as long as the reaction between the hydroxy-containing polyphenylene ether compound (a2-1-1) and the acid anhydride (a2-2-1) can proceed. As the conditions of the reaction, for example, the conditions in which the ring-opening rate of the acid anhydride (a2-2-1) is 80 to 100% are preferred. In the preliminary reaction, the acid anhydride (a2-2-1) is ring-opened by reacting with the hydroxy-containing polyphenylene ether compound (a2-1-1) as described above. Therefore, the degree of progress of the reaction can be confirmed by the ring-opening rate of the acid anhydride (a2-2-1). In the preliminary reaction product, the ring-opening rate of the acid anhydride (a2-2-1) is preferably 80 to 100% as described above. Accordingly, the amount of the acid anhydride (a2-2-1) remaining in the preliminary reaction product (A2-1) is reduced, and the adverse effects caused by the acid anhydride (a2-2-1) can be reduced. The ring-opening rate of the acid anhydride (a2-2-1) 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. -1The 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.

[0076] Opening rate (%) = {1-(A2 / B2) / (A1 / B1)}×100

[0077] Thereby, the ring-opening rate of the acid anhydride can be calculated.

[0078] It should be noted that, since the ring-opening rate of the acid anhydride (a2-2-1) 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 and confirming the ring-opening rate while performing the preliminary reaction.

[0079] 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 (a2-2-1) will volatilize before the acid anhydride (a2-2-1) reacts with the hydroxyl-containing polyphenylene ether compound (a2-1-1). Therefore, if the reaction temperature is within the above range, the hydroxyl-containing polyphenylene ether compound (a2-1-1) and the acid anhydride (a2-2-1) 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 hydroxyl-containing polyphenylene ether compound (a2-1-1) and the acid anhydride (a2-2-1) can react well.

[0080] (Preliminary reaction product (A2-2))

[0081] The pre-reaction product (A2-2) is not particularly limited as long as it is a pre-reaction product obtained by pre-reacting a mixture of a polyphenylene ether compound (a2-1-2) and a carbodiimide compound (a2-2-2) containing at least one of a hydroxyl group and a carboxyl group in the molecule. The pre-reaction product (A2-2) may be, for example, a product obtained by pre-reacting the polyphenylene ether compound (a2-1-2) and the carbodiimide compound (a2-2-2). In addition, the pre-reaction product (A2-2) may be a reaction product obtained by pre-reacting with other raw materials (a2-3-2), wherein the other raw materials (a2-3-2) are compounds that can react with at least one of the polyphenylene ether compound (a2-1-2) and the carbodiimide compound (a2-2-2). That is, examples of the pre-reaction product (A2-2) include a reaction product (A2-2-4) obtained by reacting the polyphenylene ether compound (a2-1-2) with the carbodiimide compound (a2-2-2); and a reaction product (A2-2-5) obtained by reacting the polyphenylene ether compound (a2-1-2), the carbodiimide compound (a2-2-2) and the other raw material (a2-3-2). In addition, the mixture may be a mixture containing the polyphenylene ether compound (a2-1-2) and the carbodiimide compound (a2-2-2), or a mixture further containing the other raw material (a2-3-2). The resin composition (A2-2) may contain unreacted polyphenylene ether compound (a2-1-2), may contain unreacted carbodiimide compound (a2-2-2), and may contain unreacted other raw materials (a2-3-2). In the resin composition, as the pre-reaction product (A2-2), the reaction product [at least one of the reaction product (A2-2-4) and the reaction product (A2-2-5)] may be contained, and the polyphenylene ether compound (a2-1-2) and the carbodiimide compound (a2-2-2) may also be contained. In addition, the resin composition may also contain the other raw materials (a2-3-2). It should be noted that the other raw materials (a2-3-2) are not particularly limited as long as they are compounds that can react with at least one of the polyphenylene ether compound (a2-1-2) and the carbodiimide compound (a2-2-2).

[0082] The carbodiimide compound (a2-2-2) is not particularly limited as long as it is a compound having a carbodiimide group (-N=C=N-) in the molecule. Examples of the carbodiimide compound (a2-2-2) include cyclic carbodiimide compounds. Examples of the cyclic carbodiimide compound include compounds having a carbodiimide group in the molecule and having a cyclic structure in which one nitrogen (the first nitrogen) and another nitrogen (the second nitrogen) in the carbodiimide group are bonded by a bonding group. The cyclic carbodiimide compound may be a compound having one cyclic structure or a compound having a plurality of cyclic structures.

[0083] The number of atoms forming the cyclic structure (the number of atoms in the cyclic structure) is not particularly limited, and is preferably 8 to 50, more preferably 10 to 30, further preferably 10 to 20, and particularly preferably 10 to 15, from the viewpoint of stability and easy production of the carbodiimide compound. The number of atoms in the cyclic structure refers to the number of atoms directly constituting the cyclic structure, and for example, if the cyclic structure is an 8-membered ring, the number of atoms in the cyclic structure is 8, and if the cyclic structure is a 0-membered ring, the number of atoms in the cyclic structure is 50. The molecular weight of the carbodiimide compound is not particularly limited, and is preferably 100 to 1000, more preferably 100 to 750, and further preferably 250 to 750, from the viewpoint of stability and easy production of the carbodiimide compound, as is the case with the number of atoms in the cyclic structure.

[0084] Examples of the cyclic structure include structures represented by the following formula (9). That is, examples of the carbodiimide compound include compounds containing a cyclic structure represented by the following formula (9), and more specifically, compounds represented by the following formula (9).

[0085]

[0086] In formula (9), Q represents the bonding group.

[0087] The bonding group is not particularly limited, and examples thereof include: 2-4 valent aliphatic groups, 2-4 valent alicyclic groups, 2-4 valent aromatic groups, and combinations thereof. As the aliphatic group, for example, a 2-4 valent aliphatic group with 1 to 20 carbon atoms is preferred. As the alicyclic group, for example, a 2-4 valent alicyclic group with 3 to 20 carbon atoms is preferred. As the aromatic group, for example, a 2-4 valent aromatic group with 5 to 15 carbon atoms is preferred. The bonding group may contain heteroatoms or substituents. That is, the aliphatic group, alicyclic group, and aromatic group constituting the bonding group may each contain heteroatoms or substituents. Examples of the heteroatoms include oxygen atoms, nitrogen atoms, sulfur atoms, phosphorus atoms, and halogen atoms. Examples of the substituents include alkyl groups with 1 to 20 carbon atoms, aryl groups with 6 to 15 carbon atoms, nitro groups, amide groups, hydroxyl groups, ester groups, ether groups, and aldehyde groups.

[0088] The aliphatic group is not particularly limited, and examples thereof include an alkylene group having 1 to 20 carbon atoms, an alkanetriyl group having 1 to 20 carbon atoms, and an alkanetetrayl group having 1 to 20 carbon atoms. Examples of the alkylene group include methylene, vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, dodecenyl, and hexadecenyl. Examples of the alkanetriyl group include methanetriyl, ethanetriyl, propanetriyl, butanetriyl, pentanetriyl, hexanetriyl, heptanetriyl, octanetriyl, nonanetriyl, decanetriyl, dodecanetriyl, and hexadecanetriyl. Examples of the alkanetetrayl group include methanetetrayl, ethanetetrayl, propanetetrayl, butanetetrayl, pentanetetrayl, hexanetetrayl, heptanetetrayl, octanetetrayl, nonanetetrayl, decanetetrayl, dodecanetetrayl, and hexadecanetetrayl. These aliphatic groups may also contain halogen atoms. Examples of the heteroatom include oxygen atoms, nitrogen atoms, sulfur atoms, phosphorus atoms, and halogen atoms. In addition, these aliphatic groups may also contain substituents. Examples of the substituents include alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 15 carbon atoms, nitro groups, amide groups, hydroxyl groups, ester groups, ether groups, and aldehyde groups.

[0089] The alicyclic group is not particularly limited, and examples thereof include cycloalkylene groups having 3 to 20 carbon atoms, cycloalkanetriyl groups having 3 to 20 carbon atoms, and cycloalkanetetrayl groups having 3 to 20 carbon atoms. Examples of the cycloalkylene groups include cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclononenyl, cyclodecenyl, cyclodecenyl, and cyclohexadecenyl. Examples of the alkanetriyl groups include cyclopropanetriyl, cyclobutanetriyl, cyclopentanetriyl, cyclohexanetriyl, cycloheptanetriyl, cyclooctanetriyl, cyclononanetriyl, cyclodecanetriyl, cyclododecanetriyl, and cyclohexadecanetriyl. The alkane tetrayl group includes, for example, cyclopropane tetrayl group, cyclobutane tetrayl group, cyclopentane tetrayl group, cyclohexane tetrayl group, cycloheptane tetrayl group, cyclooctane tetrayl group, cyclononane tetrayl group, cyclodecane tetrayl group, cyclododecane tetrayl group, and cyclohexadecane tetrayl group. These alicyclic groups may also contain halogen atoms and have a heterocyclic structure. The heteroatoms include, for example, oxygen atoms, nitrogen atoms, sulfur atoms, phosphorus atoms, and halogen atoms. In addition, these alicyclic groups may also contain substituents. The substituents include, for example, alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 15 carbon atoms, nitro groups, amide groups, hydroxyl groups, ester groups, ether groups, and aldehyde groups.

[0090] The aromatic group is not particularly limited, and examples thereof include arylene groups (aryl diyl groups) having 5 to 15 carbon atoms, aryl triyl groups having 5 to 15 carbon atoms, and aryl tetrayl groups having 5 to 15 carbon atoms. The arylene group is divalent, and examples thereof include phenylene and naphthalenediyl groups. The aryl triyl group is trivalent, and examples thereof include benzene triyl groups and naphthalene triyl groups. The aryl tetrayl group is tetravalent, and examples thereof include benzene tetrayl groups and naphthalene tetrayl groups. These aromatic groups may also contain halogen atoms and have aromatic heterocyclic structures. Examples of the heteroatoms include oxygen atoms, nitrogen atoms, sulfur atoms, phosphorus atoms, and halogen atoms. In addition, these aromatic groups may also contain substituents. Examples of the substituents include alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 15 carbon atoms, nitro groups, amide groups, hydroxyl groups, ester groups, ether groups, and aldehyde groups.

[0091] The above-mentioned carbodiimide compounds may be used alone or in combination of two or more.

[0092] In the reaction of the mixture containing the polyphenylene ether compound (a2-1-2) and the carbodiimide compound (a2-2-2) (the reaction of the polyphenylene ether compound (a2-1-2) and the carbodiimide compound (a2-2-2)), a catalyst may also be used. As the catalyst, there is no particular limitation as long as it is a catalyst that helps promote the reaction of the polyphenylene ether compound (a2-1-2) and the carbodiimide compound (a2-2-2). The catalyst may also be a catalyst that not only helps promote the reaction of the polyphenylene ether compound (a2-1-2) and the carbodiimide compound (a2-2-2), but also helps promote the reaction of the polyphenylene ether compound (a2-1-2) and the other raw materials (a2-3-2), and / or the reaction of the carbodiimide compound (a2-2-2) and the other raw materials (a2-3-2). As the catalyst, for example, 2-ethyl-4-methylimidazole (2E4MZ) and the like can be cited.

[0093] As the pre-reaction product (A2-2), as described above, the reaction product (A2-2-4) and the reaction product (A2-2-5) can be cited. In the reaction to obtain these reaction products, the hydroxyl group and the carboxyl group of the polyphenylene ether compound (a2-1-2) react with the carbodiimide group of the carbodiimide compound (a2-2-2), so that the polyphenylene ether compound (a2-1-2) and the carbodiimide compound (a2-2-2) are bonded. For example, the hydroxyl group reacts with the carbodiimide group to form an amide group, or the carboxyl group reacts with the carbodiimide group to form an ester bond. In addition, when the carbodiimide compound (a2-2-2) is the cyclic carbodiimide compound, the hydroxyl group and the carboxyl group of the polyphenylene ether compound (a2-1-2) act on the carbodiimide group of the carbodiimide compound (a2-2-2), and the carbodiimide compound (a2-2-2) is ring-opened to form an isocyanate group. That is, in this case, the reaction product has an isocyanate group in the molecule. For this reason, if the reaction is well performed, an isocyanate-modified polyphenylene ether compound having an isocyanate group in the molecule can be obtained. Therefore, the pre-reaction product (A2-2) preferably contains an isocyanate-modified polyphenylene ether compound whose terminal is modified by a substituent having an isocyanate group. In addition, the pre-reaction product (A2-2) may be, for example, a pre-reaction product obtained by reacting a mixture containing the hydroxyl-containing polyphenylene ether compound (a2-1-1), the acid anhydride (a2-2-1) and the carbodiimide compound (a2-2-2) in advance. In addition, the pre-reaction product (A2-2) may be, for example, a pre-reaction product obtained by reacting a mixture containing the hydroxyl-containing polyphenylene ether compound (a2-1-1) and the acid anhydride (a2-2-1) in advance, then adding the carbodiimide compound (a2-2-2) to obtain a mixture, and reacting the mixture in advance.

[0094] The reaction product is not particularly limited as long as it is at least one of the reaction product (A2-2-4) and the reaction product (A2-2-5), and examples thereof include: a compound obtained by reacting the compound represented by the formula (9) as the carbodiimide compound (a2-2-2) with the polyphenylene ether compound (a2-1-2), etc. In addition, the compound obtained by reacting the compound represented by the formula (9) as the carbodiimide compound (a2-2-2) with the polyphenylene ether compound (a2-1-2) varies depending on the structure of the polyphenylene ether compound (a2-1-2), and examples thereof include a compound represented by the following formula (10), etc.

[0095]

[0096] In formula (10), RA The following can be listed: A The same group specifically represents a hydrogen atom or an alkyl group. Q can be exemplified by the same group as Q in formula (9). 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.

[0097] The mass ratio of the polyphenylene ether compound (a2-1-2) to the carbodiimide compound (a2-2-2) (the polyphenylene ether compound (a2-1-2) / the carbodiimide compound (a2-2-2)) is preferably 20 to 200, more preferably 20 to 150, and further preferably 20 to 100. If the polyphenylene ether compound (a2-1-2) is excessive, the polyphenylene ether compound (a2-1-2) will remain excessively. Furthermore, if the carbodiimide compound (a2-2-2) is excessive, the carbodiimide compound (a2-2-2) will remain excessively, and there is a tendency that it is difficult to obtain a suitable pre-reaction product. Therefore, by mixing the polyphenylene ether compound (a2-1-2) and the carbodiimide compound (a2-2-2) in such a manner as to be within the mass ratio range, a suitable pre-reaction product can be obtained, and a resin composition and a cured product thereof having excellent performance can be obtained.

[0098] The conditions of the reaction are not particularly limited as long as the reaction of the polyphenylene ether compound (a2-1-2) and the carbodiimide compound (a2-2-2) can proceed. As the conditions of the reaction, for example, conditions where the reaction rate reaches 60 to 100% are preferred. As the conditions of the reaction, for example, when the carbodiimide compound (a2-2-2) is the cyclic carbodiimide compound, conditions where the ring-opening rate of the carbodiimide compound (a2-2-2) reaches 60 to 100% are preferred. In the preliminary reaction, the carbodiimide compound (a2-2-2) is ring-opened by reacting with the polyphenylene ether compound (a2-1-2) as described above. Therefore, the degree of progress of the reaction can be confirmed by the ring-opening rate of the carbodiimide compound (a2-2-2). In the preliminary reaction product, it is preferred that the ring-opening rate of the carbodiimide compound (a2-2-2) reaches 60 to 100% as described above. If it is this reaction rate, the hydroxyl group and carboxyl group of the polyphenylene ether compound (a2-1-2) are reduced, and the adverse effects caused by the hydroxyl group and carboxyl group can be reduced. As a result, the interlayer adhesion can be improved more well, and the decrease in interlayer adhesion caused by heating and moisture absorption can be suppressed. Therefore, a cured resin composition can be obtained that has low dielectric properties, excellent adhesion to metal foil, better interlayer adhesion, and further suppresses the decrease in interlayer adhesion caused by heating and moisture absorption. The reaction rate (for example, the ring-opening rate of the carbodiimide compound (a2-2-2)) can be calculated by comparing the infrared absorption spectra of the mixture before and after the reaction. Before the reaction (pre-reaction), the mixture may have a carbonyl group at 2060 to 2210 cm -1 In addition, the mixture may have a peak at 1450 to 1489 cm caused by the bonding group not participating in the reaction. -1 The peak near the bonding group. Then, the peak caused by the bonding group is used as an internal standard to obtain the amount (relative value) of the peak caused by the carbodiimide 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 (C1) of the peak caused by the carbodiimide group before the reaction, the area (C2) of the peak caused by the carbodiimide group after the reaction, the area (D1) of the peak caused by the bonding group before the reaction, and the area (D2) of the peak caused by the bonding group after the reaction are used. At this time, the area ratio (C1 / D1) is the amount of the carbodiimide group before the reaction, and the area ratio (C2 / D2) is the amount of the carbodiimide group after the reaction. Substitute them into the following formula.

[0099] Reaction rate (%) = {1-(C2 / D2) / (C1 / D1)) × 100

[0100] Based on this, the reaction rate (ring-opening rate of the carbodiimide compound (a2-2-2)) can be determined.

[0101] It should be noted that since the reaction rate (ring-opening rate of the carbodiimide compound (a2-2-2)) varies depending on the heating temperature and heating time when preparing the varnish, it is preferred to appropriately adjust the heating conditions to increase the ring-opening rate as much as possible, and it is more preferred to appropriately adjust the heating conditions to achieve a reaction rate of 60% 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 reaction rate.

[0102] The conditions of the reaction can be listed as the above conditions, and more specifically, the reaction temperature is preferably 30 to 150° C., and more preferably 50 to 120° C. If the reaction temperature is too low, there is a tendency that the reaction is difficult to proceed. In addition, if the reaction temperature is too high, there is a risk that the carbodiimide compound (a2-2-2) decomposes before the carbodiimide compound (a2-2-2) reacts with the polyphenylene ether compound (a2-1-2). Therefore, if the reaction temperature is within the above range, the polyphenylene ether compound (a2-1-2) and the carbodiimide compound (a2-2-2) can react well. In addition, the reaction time is preferably 1 to 8 hours, and more preferably 2 to 6 hours. If the reaction time is within the above range, the polyphenylene ether compound (a2-1-2) and the carbodiimide compound (a2-2-2) can react well.

[0103] The polyphenylene ether compound (A) can be used alone or in combination of two or more. In addition, 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 using a drill bit, laser, etc. to perform drilling. 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 permanganic acid, etc. Therefore, it is required that the substrate material used to constitute the insulating layer of the wiring board can obtain a cured product with excellent desmearing property. From the viewpoint of improving desmearing property, as the polyphenylene ether compound (A), it is preferred to include the pre-reaction product (A2-1) and the pre-reaction product (A2-2), and more preferably include the pre-reaction product (A2-1).

[0104] (Reactive compound (B))

[0105] The reactive compound (B) 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 (B) is a compound that reacts with the polyphenylene ether compound (A). The reactive compound (B) can react with the benzoxazine compound (D) described later, and is a compound different from the benzoxazine compound (D) described later. That is, the reactive compound (B) is a reactive compound having an unsaturated double bond in the molecule other than the benzoxazine compound (D) described later. In addition, the resin composition is a resin composition containing the polyphenylene ether compound (A) and the reactive compound (B). As the reactive compound (B), for example, vinyl compounds such as allyl compounds, acrylate compounds, methacrylate compounds, polybutene compounds and styrene compounds, and maleimide compounds can be cited. As for the reactive compound (B), maleimide compounds are preferred among these.

[0106] 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).

[0107] 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 di-diacrylate compounds such as tricyclodecane dimethanol diacrylate.

[0108] The methacrylate compound is a compound having a methacryloyl group in the molecule, and examples thereof include a monofunctional methacrylate compound having one methacryloyl group in the molecule and a polyfunctional methacrylate compound having two or more methacryloyl groups in the molecule. Examples of the monofunctional methacrylate compound include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate. Examples of the polyfunctional methacrylate compound include dimethacrylate compounds such as tricyclodecane dimethanol dimethacrylate (DCP), and the like.

[0109] 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.

[0110] 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.

[0111] Examples of the maleimide compound include: 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 alkylene 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 alkyl group with a carbon number of 6 or more in the molecule, and a maleimide compound having an alkyl group with a carbon number of 6 or more and an alkylene 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.

[0112] 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 metaarylene groups can be listed.

[0113] The alkyl group in the maleimide compound having at least one of an alkyl group with more than 6 carbon atoms and an alkylene group with more than 6 carbon atoms in the molecule is not particularly limited as long as it is an alkyl group with more than 6 carbon atoms, and examples thereof include hexyl, heptyl, octyl, and eicosyl. The alkylene group is not particularly limited as long as it is an alkylene group with more than 6 carbon atoms, and examples thereof include hexenyl, heptenyl octenyl, and eicosyl. The maleimide compound having at least one of an alkyl group with more than 6 carbon atoms and an alkylene group with more than 6 carbon atoms in the molecule is not particularly limited, and examples thereof include long-chain alkyl bismaleimide.

[0114] 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. In addition, as the maleimide compound having at least one of an alkyl group with a carbon number of 6 or more and an alkylene group with a carbon number of 6 or more in the molecule, BMI-1500, BMI-1700 and BMI-689 manufactured by Designer Molecules Inc. can be used.

[0115] The reactive compound (B) may be used alone or in combination of two or more.

[0116] From the viewpoint of being able to obtain a resin composition having a higher glass transition temperature, the reactive compound (B) preferably contains at least one (B1) selected from the biphenyl aralkyl maleimide compound and the polyphenylmethane maleimide [the first maleimide compound (B1)]. The reactive compound (B) more preferably contains the first maleimide compound (B1) and a maleimide compound (B2) other than the first maleimide compound (B1) [the second maleimide compound (B2)]. The second maleimide compound (B2) is preferably, for example, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, and the maleimide compound containing at least one of an alkyl group having 6 or more carbon atoms and an alkylene group having 6 or more carbon atoms in the molecule. If the reactive compound (B) contains the second maleimide compound (B2) [that is, the reactive compound (B) contains not only the first maleimide compound (B1) but also the second maleimide compound (B2)], the uniformity of the components contained in the cured product of the obtained resin composition can be further improved, and a more suitable cured product can be obtained.

[0117] When the reactive compound (B) contains the first maleimide compound (B1) and the second maleimide compound (B2), the content of the first maleimide compound (B1) 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 reactive compound (B) [relative to 100 parts by mass of the total mass of the first maleimide compound (B1) and the second maleimide compound (B2)].

[0118] When the first maleimide compound (B1) is too little, there is a tendency that the effect of using the first maleimide compound (B1) and the second maleimide compound (B2) together cannot 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, when the first maleimide compound (B1) is too much, the same as the situation that the first maleimide compound (B1) is too little, 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. Based on these reasons, by making the content of the first maleimide compound (B1) within the above range, a resin composition that obtains the following cured product is obtained, that is: the cured product has low dielectric properties, excellent adhesion to metal foil and interlayer adhesion, and the decline of interlayer adhesion caused by heating and moisture absorption is fully suppressed, and the uniformity is higher.

[0119] (Additive (C))

[0120] The additive (C) is at least one selected from the group consisting of a heavy metal deactivator (C1), a phosphite antioxidant (C2) and a hindered phenol antioxidant (C3), wherein the heavy metal deactivator (C1) has at least one of an amino group and a triazole structure and a phenolic hydroxyl group in the molecule, the phosphite antioxidant (C2) has a tert-butyl group and a phosphite structure in the molecule, and the hindered phenol antioxidant (C3) has a tert-butyl group and a phenolic hydroxyl group in the molecule. A heavy metal deactivator is a compound that forms a stable product by chelating heavy metal ions, thereby reducing the influence of heavy metal ions. It is believed that by making the resin composition contain the heavy metal deactivator (C1), even if the cured product of the resin composition contains a component that reduces interlayer adhesion, that is, heavy metal ions such as copper ions, it is possible to suppress the decrease in interlayer adhesion. Antioxidants are compounds that capture free radicals present in the system, inhibit thermal decomposition, and thus inhibit oxidative degradation. It is believed that by making the resin composition contain the phosphite antioxidant (C2), even if there are components that reduce interlayer adhesion, that is, compounds that generate free radicals, etc., the decrease in interlayer adhesion can be suppressed. It is also believed that by making the resin composition contain the hindered phenol antioxidant (C3), even if there are components that reduce interlayer adhesion, that is, compounds that generate free radicals, etc., the decrease in interlayer adhesion can be suppressed. In addition, from the viewpoint of obtaining a cured product that further suppresses the decrease in interlayer adhesion caused by heating and moisture absorption, the additive (C) is preferably used in combination with: at least one of the phosphite antioxidant (C2) and the hindered phenol antioxidant (C3); and the heavy metal deactivator (C1).

[0121] The heavy metal deactivator (C1) is not particularly limited as long as it has at least one of an amino group and a triazole structure and a phenolic hydroxyl group in the molecule. Examples of the heavy metal deactivator (C1) include heavy metal deactivators having an amino group and a phenolic hydroxyl group in the molecule, heavy metal deactivators having a triazole structure and a phenolic hydroxyl group in the molecule, and heavy metal deactivators having an amino group, a triazole structure, and a phenolic hydroxyl group in the molecule. Specifically, examples of the heavy metal deactivator (C1) include 2-hydroxy-N-1H-1,2,4-triazole-3-ylbenzamide (for example, ADK STAB CDA-1 manufactured by ADK Co., Ltd.).

[0122] The phosphite antioxidant (C2) is not particularly limited as long as it has a tert-butyl group (tertiary butyl group) and a phosphite structure in the molecule. Specific examples of the phosphite antioxidant (C2) include 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane (e.g., ADK STAB PEP-36 manufactured by ADICO Co., Ltd.), 2,2'-methylenebis(4,6-di-tert-butyl-1-diphenoxy)(2-ethylhexyloxy)phosphite (e.g., ADK STAB HP-10 manufactured by ADICO Co., Ltd.), and tris(2,4-di-tert-butylphenyl) phosphite (e.g., ADK STAB 2112 and 2112RG manufactured by ADICO Co., Ltd.).

[0123] The hindered phenol antioxidant (C3) is not particularly limited as long as it is a hindered phenol antioxidant having a tert-butyl group and a phenolic hydroxyl group in the molecule. Specific examples of the hindered phenol antioxidant (C3) include 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (e.g., ADK STAB A0-20 manufactured by ADICO Co., Ltd.), octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (e.g., ADK STAB AO-50, AO-50F and AO-50T manufactured by ADICO Co., Ltd.), pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (e.g., ADK STAB A0-50, AO-50F and AO-50T manufactured by ADICO Co., Ltd.), and 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (e.g., ADK STAB A0-50, AO-50F and AO-50T manufactured by ADICO Co., Ltd.). AO-60 and AO-60G, etc.), and 1,3,5-tris(3,5-tert-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene (for example, ADKSTAB AO-330 manufactured by ADK CORPORATION, etc.).

[0124] The additives (C) may be used alone or in combination of two or more.

[0125] (Benzoxazine compound (D))

[0126] The resin composition may contain a benzoxazine compound (D). The benzoxazine compound (D) is not particularly limited as long as it is a compound having a benzoxazine ring in the molecule, and the benzoxazine compound (D) also includes, for example, a benzoxazine resin, etc. It should be noted that the benzoxazine compound (D) is a compound that reacts with at least one of the polyphenylene ether compound (A) and the reactive compound (B). In addition, the benzoxazine compound (D) is a compound different from the reactive compound (B). As the benzoxazine compound (D), for example, a benzoxazine compound having a phenolphthalein structure in the molecule (phenolphthalein type benzoxazine compound), a benzoxazine compound having an alkenyl group in the molecule, a bisphenol F type benzoxazine compound, and a diaminodiphenylmethane (DDM) type benzoxazine compound, etc. can be cited. More specifically, the benzoxazine compound (D) includes 3,3′-(methylene-1,4-diphenylene)bis(3,4-dihydro-2H-1,3-benzoxazine) (Pd-type benzoxazine compound), and 2,2-bis(3,4-dihydro-2H-3-phenyl-1,3-benzoxazine)methane (Fa-type benzoxazine compound).

[0127] The benzoxazine compound (D) is preferably a benzoxazine compound having an alkenyl group in the molecule among the exemplified benzoxazine compounds. The benzoxazine compound having an alkenyl group in the molecule 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. The alkenyl group is not particularly limited, and examples thereof include alkenyl groups having 2 to 6 carbon atoms. Specifically, vinyl, allyl, and butenyl groups may be mentioned, among which allyl groups are preferred. In addition, as the benzoxazine compound (D), for example, compounds having a benzoxazine group (the benzoxazine group having an alkenyl group) in the molecule may be mentioned. As the benzoxazine group (benzoxazine group having an alkenyl group), for example, a benzoxazine group represented by the following formula (11) and a benzoxazine group represented by the following formula (12) may be mentioned. Examples of the benzoxazine compound (D) include a benzoxazine compound having a benzoxazine group represented by the following formula (11) in the molecule, a benzoxazine compound having a benzoxazine group represented by the following formula (12) in the molecule, and a benzoxazine compound having a benzoxazine group represented by the following formula (11) and a benzoxazine group represented by the following formula (12) in the molecule. Examples of the benzoxazine compound having a benzoxazine group represented by the following formula (11) in the molecule include a benzoxazine compound represented by the following formula (13).

[0128]

[0129] In formula (11), R39 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.

[0130]

[0131] In formula (12), R 40 It represents an alkenyl group.

[0132]

[0133] In formula (13), 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.

[0134] The alkenyl group in the formulae (11) to (13) is not particularly limited as described above, but is preferably an allyl group.

[0135] 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.

[0136] 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.

[0137] As the benzoxazine compound (D), a commercially available product may be used, and for example, ALPd manufactured by Shikoku Chemicals Co., Ltd. may be used.

[0138] As the benzoxazine compound (D), the benzoxazine compounds exemplified above may be used alone or in combination of two or more.

[0139] (content)

[0140] The content of the polyphenylene ether compound (A) is not particularly limited, and is preferably 20 to 80 parts by mass, more preferably 25 to 80 parts by mass, and further preferably 30 to 80 parts by mass, relative to 100 parts by mass of the total of the polyphenylene ether compound (A) and the reactive compound (B). When the benzoxazine compound (D) is contained in the resin composition, the content of the polyphenylene ether compound (A) is not particularly limited, and is preferably 20 to 80 parts by mass, more preferably 20 to 75 parts by mass, and further preferably 25 to 70 parts by mass, relative to 100 parts by mass of the total of the polyphenylene ether compound (A), the reactive compound (B), and the benzoxazine compound (D).

[0141] The content of the reactive compound (B) is not particularly limited, and is preferably 20 to 80 parts by mass, more preferably 20 to 75 parts by mass, and further preferably 20 to 70 parts by mass, relative to 100 parts by mass of the total of the polyphenylene ether compound (A) and the reactive compound (B). In the case where the resin composition contains the benzoxazine compound (D), the content of the reactive compound (B) is not particularly limited, and is preferably 20 to 75 parts by mass, more preferably 25 to 75 parts by mass, and further preferably 25 to 70 parts by mass, relative to 100 parts by mass of the total of the polyphenylene ether compound (A), the reactive compound (B) and the benzoxazine compound (D). When the resin composition contains the benzoxazine compound (D) and the reactive compound (B) contains a maleimide compound (when the reactive compound (B) is a maleimide compound), the content of the maleimide compound is not particularly limited, but is preferably 20 to 75 parts by mass, more preferably 25 to 75 parts by mass, and even more preferably 25 to 70 parts by mass, relative to 100 parts by mass of the total of the polyphenylene ether compound (A), the reactive compound (B) and the benzoxazine compound (D).

[0142] The content of the additive (C) is not particularly limited, and is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 8 parts by mass, and further preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the total of the polyphenylene ether compound (A) and the reactive compound (B). In the case where the resin composition contains the benzoxazine compound (D), the content of the additive (C) is not particularly limited, and is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 8 parts by mass, and further preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the total of the polyphenylene ether compound (A), the reactive compound (B) and the benzoxazine compound (D).

[0143] When the resin composition contains the benzoxazine compound (D), the content of the benzoxazine compound (D) 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 polyphenylene ether compound (A), the reactive compound (B) and the benzoxazine compound (D).

[0144] If the polyphenylene ether compound (A) is too little, that is, the total of the reactive compound (B) and the benzoxazine compound (D) is too much, there is a tendency that it is difficult to maintain excellent low dielectric properties such as the relative dielectric constant becomes high, or it is difficult to remove smear. In addition, if the polyphenylene ether compound (A) is too much, that is, the total of the reactive compound (B) and the benzoxazine compound (D) is too little, there is a tendency that it is easy to remove smear too much. That is, if the reactive compound (B) is too little, or the benzoxazine compound (D) is too little, there is a tendency that it is easy to remove smear too much. In addition, if the reactive compound (B) is too much, or the benzoxazine compound (D) is too much, there is a tendency that it is difficult to maintain excellent low dielectric properties such as the relative dielectric constant becomes high, or it is difficult to remove smear.

[0145] If the amount of the additive (C) is too little, the effect exerted by adding the additive (C) is insufficient, and for example, there is a tendency that the decrease in interlayer adhesion due to heating and moisture absorption cannot be sufficiently suppressed. In addition, if the amount of the additive (C) is too much, there is also a tendency that the effect exerted by adding the additive (C) is saturated. In addition, if the amount of the additive (C) is too much, there is a tendency that at least one of the polyphenylene ether compound (A), the reactive compound (B) and the benzoxazine compound (D) is reduced, and in this case, there is a tendency that an undesirable situation caused by the reduction of any one component occurs.

[0146] Therefore, if the contents of the polyphenylene ether compound (A), the reactive compound (B), the additive (C) and the benzoxazine compound (D) are within the above ranges, a cured product can be obtained which has excellent adhesion to metal foil, interlayer adhesion and desmearing properties, and in which a decrease in interlayer adhesion due to heating and moisture absorption is sufficiently suppressed, that is, a cured product in which the ease of desmearing can be well adjusted while maintaining excellent low dielectric properties.

[0147] (Inorganic filler)

[0148] 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.

[0149] 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.

[0150] 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.

[0151] 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.

[0152] 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.

[0153] 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 not particularly limited, and is preferably 10 to 250 parts by mass, and more preferably 40 to 200 parts by mass, relative to 100 parts by mass of the total mass of the polyphenylene ether compound (A) and the reactive compound (B). When the resin composition contains the benzoxazine compound (D) and the inorganic filler, the content of the inorganic filler is not particularly limited, and is preferably 10 to 250 parts by mass, and more preferably 40 to 200 parts by mass, relative to 100 parts by mass of the total mass of the polyphenylene ether compound (A), the reactive compound (B) and the benzoxazine compound (D).

[0154] (Other ingredients)

[0155] The resin composition involved in the present embodiment may also contain components (other components) other than the polyphenylene ether compound (A), the reactive compound (B) and the benzoxazine compound (D) 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 (B), 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.

[0156] The resin composition involved in this embodiment may also contain reactive compounds (other reactive compounds) other than the reactive compound (B). The other reactive compound is a compound different from the reactive compound (B) and the benzoxazine compound (D). The other reactive compound is not particularly limited, and examples thereof include acenaphthylene compounds, cyanate compounds, and active ester compounds. The other reactive compounds may be used alone or in combination of two or more.

[0157] 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.

[0158] 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.

[0159] 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.

[0160] 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.

[0161] 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 salts such as tetraphenylphosphonium ethyltriphenylborate. 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.

[0162] 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.

[0163] 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.

[0164] (use)

[0165] 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.

[0166] (Manufacturing method)

[0167] The method for producing the resin composition is not particularly limited, and examples thereof include a method of mixing the polyphenylene ether compound (A), the reactive compound (B), the additive (C), and the benzoxazine compound (D) under conditions of achieving a predetermined content, etc. In addition, in the case of obtaining a varnish-like composition containing an organic solvent, the method described below, etc., can be used.

[0168] 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.

[0169] [Prepreg]

[0170] Figure 1 This is a schematic cross-sectional view showing an example of the prepreg 1 according to the embodiment of the present invention.

[0171] 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.

[0172] 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.

[0173] 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 heating the resin composition.

[0174] 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.

[0175] First, each component soluble in an organic solvent is put into an organic solvent and dissolved. At this time, heating can be performed as needed. Then, a component insoluble in an organic solvent used as needed is added, and a ball mill, a bead mill, a planetary mixer, a roller mill, etc. are used to disperse it to a specified dispersed state, thereby modulating a varnish-like resin composition. As the organic solvent used herein, as long as it is an organic solvent that can dissolve the polyphenylene ether compound (A) and the reactive compound (B) and the like and does not hinder the curing reaction, it is not particularly limited. Specifically, for example, toluene, methyl ethyl ketone (MEK), etc. can be cited.

[0176] 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.

[0177] 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.

[0178] 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.

[0179] 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.

[0180] The resin combination that the present embodiment is related to is the resin combination that can obtain low dielectric properties, excellent adhesion and interlayer adhesion with metal foil, and fully suppresses the cured product of the decline of interlayer adhesion caused by heating and moisture absorption.Therefore, the prepreg possessing the semi-cured product of this resin combination or this resin combination is the prepreg that can obtain low dielectric properties, excellent adhesion and interlayer adhesion with metal foil, and fully suppresses the cured product of the decline of interlayer adhesion caused by heating and moisture absorption.And, this prepreg can well manufacture the wiring board of the insulating layer of the cured product that comprises low dielectric properties, excellent adhesion and interlayer adhesion with metal foil, and fully suppresses the decline of interlayer adhesion caused by heating and moisture absorption.

[0181] [Metal foil laminate]

[0182] 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.

[0183] 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.

[0184] 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.

[0185] The resin composition involved in the present embodiment is a resin composition that can obtain a low dielectric property, excellent adhesion to metal foil and interlayer adhesion, and fully suppresses the curing material of the decline of interlayer adhesion caused by heating and moisture absorption. Therefore, the metal foil clad laminated board having an insulating layer of a cured product comprising the resin composition is a metal foil clad laminated board having an insulating layer of a cured product comprising low dielectric property, excellent adhesion to metal foil and interlayer adhesion, and fully suppresses the curing material of the decline of interlayer adhesion caused by heating and moisture absorption. And, the metal foil clad laminated board can well manufacture a wiring board having an insulating layer of a cured product comprising low dielectric property, excellent adhesion to metal foil and interlayer adhesion, and fully suppresses the curing material of the decline of interlayer adhesion caused by heating and moisture absorption.

[0186] [Wiring board]

[0187] Figure 3 It is a schematic cross-sectional view showing an example of wiring board 21 according to the embodiment of the present invention.

[0188] 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.

[0189] 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.

[0190] The wiring board 21 is a wiring board including an insulating layer 12 made of a cured product having low dielectric properties, excellent adhesion to metal foil and interlayer adhesion, and in which a decrease in interlayer adhesion due to heating and moisture absorption is sufficiently suppressed.

[0191] [Metal foil with resin]

[0192] Figure 4 It is a schematic cross-sectional view showing an example of the metal foil with resin 31 according to the present embodiment.

[0193] 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.

[0194] 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.

[0195] As the metal foil, metal foils used in metal foil-clad laminates and metal foils with resins can be used without limitation. Examples of the metal foil include copper foil and aluminum foil.

[0196] 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.

[0197] 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 manufacturing by 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.

[0198] The resin composition involved in the present embodiment is a resin composition of a cured product that can obtain low dielectric properties, excellent adhesion to metal foil and interlayer adhesion, and fully suppresses the decline of interlayer adhesion caused by heating and moisture absorption. Therefore, the metal foil with resin having a resin layer containing the resin composition or the semi-cured product of the resin composition is a metal foil with resin having a resin layer of a cured product that can obtain low dielectric properties, excellent adhesion to metal foil and interlayer adhesion, and fully suppresses the decline of interlayer adhesion caused by heating and moisture absorption. In addition, the metal foil with resin can be used when manufacturing a wiring board having an insulating layer of a cured product containing low dielectric properties, excellent adhesion to metal foil and interlayer adhesion, and. fully suppresses the decline of interlayer adhesion caused by heating and moisture absorption. For example, a multilayer wiring board can be manufactured by stacking on a wiring board. A wiring board obtained by using the metal foil with resin can be obtained which has an insulating layer including a cured product having low dielectric properties, excellent adhesion to the metal foil and interlayer adhesion, and in which a decrease in interlayer adhesion due to heating and moisture absorption is sufficiently suppressed.

[0199] [Film with resin]

[0200] Figure 5 It is a schematic cross-sectional view showing an example of the film 41 with resin according to the present embodiment.

[0201] 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.

[0202] 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.

[0203] 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.

[0204] 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.

[0205] 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.

[0206] 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.

[0207] The resin composition involved in the present embodiment is a resin composition that can obtain low dielectric properties, excellent adhesion to metal foil and interlayer adhesion, and fully suppresses the curing material of the decline of interlayer adhesion caused by heating and moisture absorption. 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 curing material that can obtain low dielectric properties, excellent adhesion to metal foil and interlayer adhesion, and fully suppresses the decline of interlayer adhesion caused by heating and moisture absorption. And, the film with resin can be used when manufacturing the wiring board with the insulating layer of the curing material that comprises low dielectric properties, excellent adhesion to metal foil and interlayer adhesion, and fully suppresses the decline of interlayer adhesion caused by heating and moisture absorption. For example, it is possible to peel off the supporting film after being stacked on the wiring board, or, after peeling off the supporting film, it is stacked on the wiring board to manufacture a multilayer wiring board. A wiring board obtained using the film with the resin can be obtained which includes an insulating layer having a cured product having low dielectric properties, excellent adhesion to metal foil and interlayer adhesion, and in which a decrease in interlayer adhesion due to heating and moisture absorption is sufficiently suppressed.

[0208] As described above, this specification discloses the technologies of various embodiments, and the main technologies are summarized as follows.

[0209] The first technical solution relates to a resin composition, which contains: a polyphenylene ether compound (A); a reactive compound (B) having an unsaturated double bond in the molecule; and at least one additive (C) selected from the group consisting of a heavy metal deactivator (C1), a phosphite antioxidant (C2) and a hindered phenol antioxidant (C3), wherein the heavy metal deactivator (C1) has at least one of an amino group and a triazole structure, and a phenolic hydroxyl group in the molecule, the phosphite antioxidant (C2) has a tert-butyl group and a phosphite structure in the molecule, and the hindered phenol antioxidant (C3) has a tert-butyl group and a phenolic hydroxyl group in the molecule.

[0210] The resin composition involved in the second technical solution is the resin composition involved in the first technical solution, wherein the polyphenylene ether compound (A) contains at least one of a polyphenylene ether compound (A1) and a pre-reaction product (A2), wherein the polyphenylene ether compound (A1) has at least one selected from the group consisting of a hydroxyl group, a carboxyl group, an unsaturated double bond group and an ester bond in the molecule, and the pre-reaction product (A2) is obtained by preliminarily reacting a mixture containing a polyphenylene ether compound (a2-1) and a compound (a2-2), wherein the polyphenylene ether compound (a2-1) has at least one selected from the group consisting of a hydroxyl group, a carboxyl group and an ester bond in the molecule, and the compound (a2-2) reacts with at least one of the hydroxyl group, the carboxyl group and the ester bond.

[0211] The resin composition according to the third aspect is the resin composition according to the second aspect, wherein the preliminary reaction product (A2) includes a preliminary reaction product obtained by previously reacting a polyphenylene ether compound having a hydroxyl group in its molecule with an acid anhydride having an acid anhydride group in its molecule.

[0212] A resin composition according to a fourth aspect is the resin composition according to any one of the first to third aspects, wherein the reactive compound (B) contains at least one selected from the group consisting of allyl compounds, acrylate compounds, methacrylate compounds, polybutadiene compounds, styrene compounds, and maleimide compounds.

[0213] The resin composition according to the fifth invention is the resin composition according to any one of the first to fourth inventions, wherein the content of the polyphenylene ether compound (A) is 20 to 80 parts by mass based on 100 parts by mass of the total of the polyphenylene ether compound (A) and the reactive compound (B).

[0214] The resin composition according to the sixth invention is the resin composition according to any one of the first to fifth inventions, further comprising a benzoxazine compound (D).

[0215] The resin composition according to the seventh technical solution is the resin composition according to any one of the first to sixth technical solutions, wherein the additive (C) comprises: at least one of the phosphite antioxidant (C2) and the hindered phenol antioxidant (C3); and the heavy metal deactivator (C1).

[0216] The resin composition according to the eighth invention is the resin composition according to any one of the first to seventh inventions, further comprising an inorganic filler.

[0217] The resin composition according to a ninth aspect is the resin composition according to the eighth aspect, wherein the inorganic filler is surface-treated with a silane coupling agent.

[0218] A tenth technical solution is directed to a prepreg comprising: the resin composition according to any one of the first to ninth technical solutions or a semi-cured product of the resin composition; and a fibrous base material.

[0219] The eleventh invention relates to a film with a resin, comprising: a resin layer containing the resin composition according to any one of the first to ninth inventions or a semi-cured product of the resin composition; and a support film.

[0220] A twelfth invention relates to a film with a resin, comprising: a resin layer containing the resin composition according to any one of the first to ninth inventions or a semi-cured product of the resin composition; and a metal foil.

[0221] A thirteenth 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 ninth inventions; and a metal foil.

[0222] A fourteenth invention relates to a metal foil-clad laminate comprising: an insulating layer formed of a cured product of the prepreg according to the tenth invention; and a metal foil.

[0223] A fifteenth 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 ninth inventions; and wiring.

[0224] A sixteenth invention relates to a wiring board comprising: an insulating layer formed of a cured product of the prepreg according to the tenth invention; and wiring.

[0225] According to the present invention, a resin composition can be provided that can obtain a cured product having low dielectric properties, excellent adhesion to metal foil and interlayer adhesion, and fully suppressing the decrease in interlayer adhesion caused by heating and moisture absorption. 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.

[0226] 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.

[0227] Example

[0228] [Examples 1 to 7, Comparative Examples 1 and 2]

[0229] Each component used to prepare the resin composition in this example is described.

[0230] (Polyphenylene ether compound (A))

[0231] Pre-reaction product: A pre-reaction product obtained by reacting a polyphenylene ether compound having a hydroxyl group in the molecule with an acid anhydride having an acid anhydride group in the molecule in advance.

[0232] Specifically, the preliminary reaction product is a preliminary reaction product obtained by the following reaction.

[0233] The components used in producing the preliminary reaction product will be described.

[0234] Polyphenylene ether compound having hydroxyl groups in the molecule: SA90 manufactured by SABIC Innovative Plastics, with 2 terminal hydroxyl groups, number average molecular weight Mn1700, phenol equivalent (hydroxyl equivalent) 850 g / eq

[0235] Acid anhydride: 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)

[0236] First, 84 parts by mass of the polyphenylene ether compound (SA90) having a hydroxyl group in the molecule and 16 parts by mass of the acid anhydride (RIKACID MH-700) were mixed and diluted with toluene so that the solid content concentration became 40% by mass. The mixture was stirred and mixed for 5 hours at a liquid temperature of 30° C. using a disperser. Through this operation, the polyphenylene ether compound having a hydroxyl group in the molecule and the acid anhydride reacted to obtain a pre-reaction product. The ring-opening rate of the obtained pre-reaction product (the ring-opening rate obtained by the above-mentioned calculation method) was 91%.

[0237] It should be noted that the equivalent ratio of the hydroxyl group of the polyphenylene ether compound having a hydroxyl group in the molecule to the anhydride group of the acid anhydride is calculated based on the functional group (reactive group) that reacts. That is, the equivalent ratio recorded in Table 1 is calculated as the ratio of the values ​​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, etc., but a ratio obtained by rounding off or the like to appropriately approximate the value. That is, the equivalent ratio recorded in Table 1 is a ratio approximated by rounding off the ratio of the values ​​obtained by dividing each mixed amount by the equivalent of each functional group. Specifically, the phenol equivalent (hydroxyl equivalent) of the polyphenylene ether compound having a hydroxyl group in the molecule is 850 g / eq, and the functional group equivalent of the anhydride group of the acid anhydride is 161 to 166 g / eq. It should be noted that the functional group equivalent of the anhydride group of the acid anhydride is assumed to be 163 g / eq for calculation. The mixing amount of the polyphenylene ether compound having a hydroxyl group in the molecule is 84 parts by mass, and the mixing amount of the acid anhydride is 16 parts by mass. Based on these data, it can be calculated that the equivalent ratio (hydroxyl equivalent of the polyphenylene ether compound having a hydroxyl group in the molecule: anhydride group equivalent of the acid anhydride) is (84 / 850): (16 / 163) = about 1:1. Therefore, the equivalent ratio in the pre-reaction product is 1:1. That is, the equivalent ratio of the anhydride group of the acid anhydride to the hydroxyl group of the polyphenylene ether compound having a hydroxyl group in the molecule is 1.

[0238] The preliminary reaction product thus obtained is a preliminary reaction product obtained by reacting in advance a mixture containing the polyphenylene ether compound having a hydroxyl group in the molecule and the acid anhydride (ester and carboxyl-modified polyphenylene ether compound whose terminal is modified with a substituent having an ester bond and a carboxyl group: a polyphenylene ether compound having a carboxyl group).

[0239] Modified PPE: a polyphenylene ether compound (styrene-modified polyphenylene ether) having a vinylbenzyl group (vinylbenzyl) at a molecular terminal (OPE-1200 manufactured by Mitsubishi Gas Chemical Co., Ltd., number average molecular weight Mn 1200, functional group equivalent of vinylbenzyl group 670 g / eq)

[0240] (Reactive compound (B))

[0241] 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)

[0242] 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)

[0243] (Benzoxazine compound (D))

[0244] Benzoxazine compound: a benzoxazine compound having an allyl group as an alkenyl group in the molecule (an alkenyl-containing benzoxazine compound represented by the formula (13) wherein 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)

[0245] (Additive (C))

[0246] Heavy metal deactivator: 2-hydroxy-N-1H-1,2,4-triazol-3-ylbenzamide (ADK STAB CDA-1 manufactured by ADK Co., Ltd.)

[0247] Phosphite antioxidant: 2,2'-methylenebis(4,6-di-tert-butyl-1-diphenoxy)(2-ethylhexyloxy)phosphite (ADK STAB HP-10 manufactured by ADK Corporation)

[0248] (Curing accelerator)

[0249] 2E4MZ: Imidazole curing accelerator (2-ethyl-4-methylimidazole, 2E4MZ manufactured by Shikoku Chemical Industry Co., Ltd.)

[0250] (Inorganic filler)

[0251] Inorganic filler: Spherical silica surface-treated with vinyl silane (SC2300-SVJ manufactured by Admatechs Company Limited)

[0252] (Preparation method)

[0253] First, the components other than the inorganic filler are added to methyl ethyl ketone (MEK) in a manner such that the solid content concentration is 60% by mass according to the composition (mass parts) described in Table 1, and stirred and mixed using a disperser to make it uniform. The inorganic filler is added to the uniform mixture according to the composition (mass parts) described in Table 1, and stirred and mixed using a disperser for 2 hours to make it uniform. By doing so, a varnish-like resin composition (varnish) is obtained.

[0254] Next, a prepreg and evaluation substrates 1 and 2 (metal foil-clad laminates) were obtained as follows.

[0255] 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.

[0256] Next, an evaluation substrate 1 (metal foil-clad laminate) was obtained in the following manner.

[0257] Copper foil (Mitsui Mining & Smelting Co., Ltd., 35 μm thick, ST foil, one side surface is rough) was arranged on both sides of each obtained prepreg, 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 0.1 mm and copper foil bonded to both sides.

[0258] Next, an evaluation substrate 2 (metal foil-clad laminate) was obtained in the following manner.

[0259] 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 2: metal-clad laminate) with a thickness of about 0.6 mm and copper foil bonded to both sides.

[0260] Next, an evaluation substrate 3 (metal foil-clad laminate) was obtained in the following manner.

[0261] Eight 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 3: metal-clad laminate) with a thickness of about 0.8 mm and copper foil bonded to both sides.

[0262] Evaluation substrates 1 to 3 (copper-clad laminates) prepared as described above were evaluated by the methods shown below.

[0263] [Copper foil peel strength]

[0264] The copper foil was peeled off from the evaluation substrate 1 (metal foil-clad laminate), and the peel strength at this 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 this time was measured. This peel strength is the copper foil peel strength, and it is known that the higher the peel strength, the higher the adhesion of the metal foil (copper foil).

[0265] [Interlayer peel strength]

[0266] The copper foil was removed from the evaluation substrate 1 (metal foil laminate) by etching, thereby obtaining a bare board. The bare board was used as a core material, and prepregs were arranged on both sides of the surface to obtain a laminated body that had been subjected to secondary molding. The uppermost insulating layer (prepreg) was peeled off from the laminated body at a speed of 50 mm / min using a tensile testing machine, and the peel strength (N / mm) at this time was measured. The peel strength is the interlayer peel strength in the normal state, and it can be seen that the higher the peel strength, the higher the interlayer adhesion in the normal state (i.e., when neither moisture absorption treatment nor heat treatment is performed).

[0267] [Interlayer peel strength after moisture absorption treatment]

[0268] The copper foil was removed from the evaluation substrate 1 (metal foil-clad laminate) by etching, thereby obtaining a bare board. The bare board was used as a core material, and prepregs were arranged on both sides of the surface to obtain a laminate that had been subjected to secondary molding. The laminate was subjected to a moisture absorption treatment at 121°C and a relative humidity of 100% for 72 hours, and the uppermost insulating layer (prepreg) was peeled off from the laminate that had been subjected to moisture absorption treatment using a tensile testing machine at a speed of 50 mm / min, and the peel strength (N / mm) at this time was measured. The peel strength is the interlayer peel strength after the moisture absorption treatment, and it can be seen that the higher the peel strength, the higher the interlayer adhesion after the moisture absorption treatment.

[0269] [Interlayer peel strength after heat treatment]

[0270] The copper foil was removed from the evaluation substrate 1 (metal foil laminate) by etching, thereby obtaining a bare board. The bare board was used as a core material, and prepregs were arranged on both sides of the surface to obtain a laminated body that had been subjected to secondary molding. The laminated body was subjected to a heat treatment at 260°C and a relative humidity of 0% for 1 hour, and the uppermost insulating layer (prepreg) was peeled off from the laminated body that had been subjected to the heat treatment at a speed of 50 mm / min using a tensile testing machine, and the peel strength (N / mm) at this time was measured. The peel strength is the interlayer peel strength after the heat treatment, and it can be seen that the higher the peel strength, the higher the interlayer adhesion after the heat treatment.

[0271] [Desmearing property]

[0272] First, the copper foil on the surface of the evaluation substrate 2 (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. The weight of the substrate was measured before and after the desmearing step, and the weight reduced by the desmearing step was calculated (the weight of the substrate before the desmearing step minus the weight of the substrate after the desmearing step). Further, based on the reduced weight, the weight per 1 mm 2 Weight loss (mg / mm 2 ). 2 The weight reduction was evaluated as follows.

[0273] If every 1mm 2 The weight loss is less than 15mg / mm 2 , the evaluation is "A (×)", if it is 15mg / mm 2More than and less than 30mg / mm 2 , the evaluation is "B (○)", if 30mg / mm 2 More than and less than 45mg / mm 2 , the evaluation is "C (◎)", if it is 45mg / mm 2 If the value is greater than or equal to 0, the evaluation is "D (×)".

[0274] It should be noted that "A (×)" is not preferred from the viewpoint of difficulty in removing smear, and "D (×)" is not preferred from the viewpoint of not being able to maintain the shape of the through hole, etc., because the resin is removed excessively. In contrast, "B (○)" and "C (◎)" are preferred from the viewpoint of being able to remove smear while maintaining the shape of the through hole, etc., and from this point of view, "C (◎)" is more preferred.

[0275] [Relative dielectric constant Dk]

[0276] The bare board from which the copper foil was removed from the evaluation substrate 3 (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 3) at 1 GHz was measured according to IPC-TM-650 2.5.5.9 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.

[0277] Table 1 shows the results of the above-mentioned evaluations.

[0278] Table 1

[0279]

[0280] As shown in Table 1, in the resin composition containing the polyphenylene ether compound (A) and the reactive compound (B), when the additive (C) is contained (Examples 1 to 7), a cured product having the same or higher copper foil peeling strength and interlayer peeling strength as when the additive (C) is not contained (Comparative Examples 1 and 2) can be obtained. In addition, as described above, Examples 1 to 7 not only have high copper foil peeling strength and interlayer peeling strength, but also have high interlayer peeling strength after moisture absorption treatment and interlayer peeling strength after heat treatment compared to when the additive (C) is not contained (Comparative Examples 1 and 2). Specifically, it is more clearly known that, compared with the case where the content of the polyphenylene ether compound (A) and the reactive compound (B) is the same, when the additive (C) is contained, not only the copper foil peeling strength and interlayer peeling strength are high, but also the interlayer peeling strength after moisture absorption treatment and interlayer peeling strength after heat treatment can be obtained compared to when the additive (C) is not contained. More specifically, it can be seen that: compared with Comparative Example 1, Examples 1 and 2 can obtain a cured product having not only high copper foil peeling strength and interlayer peeling strength, but also high interlayer peeling strength after moisture absorption treatment and interlayer peeling strength after heat treatment. In addition, it can be seen that, compared with Comparative Example 2, Examples 3 and 4 can obtain a cured product having not only high copper foil peeling strength and interlayer peeling strength, but also high interlayer peeling strength after moisture absorption treatment and interlayer peeling strength after heat treatment. In addition, the relative dielectric constants of Examples 1 to 7 are low, being less than 3.4, from which it can be seen that a cured product having excellent low dielectric properties can be obtained. According to these results, by containing the additive (C), a resin composition can be obtained that becomes a cured product having low dielectric properties, excellent adhesion to metal foil and interlayer adhesion, and fully suppressing the decrease in interlayer adhesion caused by heating and moisture absorption.

[0281] It can be seen that when the heavy metal deactivator (C1) and the phosphite antioxidant (C2) are used together as the additive (C) (Example 5), compared with the case where the content of the additive (C) is the same and either the heavy metal deactivator (C1) or the phosphite antioxidant (C2) is used as the additive (C) (Examples 1 and 3), a resin composition can be obtained that is a cured product having excellent adhesion to metal foil and interlayer adhesion and suppressing a decrease in interlayer adhesion due to heating and moisture absorption. It can be seen that as the additive (C), it is preferable to use the heavy metal deactivator (C1) and the phosphite antioxidant (C2) together.

[0282] Examples 1 to 6 are resin compositions containing a pre-reaction product obtained by reacting a polyphenylene ether compound having a hydroxyl group in the molecule and an acid anhydride having an acid anhydride group in the molecule as the polyphenylene ether compound (A). It can be seen that when such a pre-reaction product is contained (Examples 1 to 6), a cured product with excellent desmearing property is obtained compared with when the pre-reaction product is not contained and a polyphenylene ether compound other than the pre-reaction product is contained (Example 7). It can be seen that by containing the pre-reaction product as the polyphenylene ether compound (A), a cured product can be obtained that not only has low dielectric properties, excellent adhesion to metal foil and interlayer adhesion, and fully suppresses the decrease in interlayer adhesion due to heating and moisture absorption, but also has excellent desmearing property. It should be noted that Example 7 is not easy to remove smear compared with Examples 1 to 6, but it is an excellent resin composition that becomes a cured product with low dielectric properties, excellent adhesion to metal foil and interlayer adhesion, and fully suppresses the decrease in interlayer adhesion caused by heating and moisture absorption.

[0283] This application is based on Japanese patent application No. 2022-134867 filed on August 26, 2022, and the contents are incorporated herein by reference.

[0284] 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.

[0285] Industrial Applicability

[0286] According to the present invention, a resin composition can be provided that can obtain a cured product having low dielectric properties, excellent adhesion to metal foil and interlayer adhesion, and fully suppressing the decrease in interlayer adhesion caused by heating and moisture absorption. 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 polyphenylene ether compound (A); a reactive compound (B) having an unsaturated double bond in the molecule; and At least one additive (C) selected from the group consisting of a heavy metal deactivator (C1), a phosphite antioxidant (C2) and a hindered phenol antioxidant (C3), wherein: The heavy metal deactivator (C1) has at least one of an amino group and a triazole structure, and a phenolic hydroxyl group in the molecule, the phosphite antioxidant (C2) has a tert-butyl group and a phosphite structure in the molecule, and the hindered phenol antioxidant (C3) has a tert-butyl group and a phenolic hydroxyl group in the molecule.

2. The resin composition according to claim 1, characterized in that The polyphenylene ether compound (A) contains at least one of a polyphenylene ether compound (A1) and a pre-reaction product (A2), wherein: The polyphenylene ether compound (A1) has at least one selected from the group consisting of a hydroxyl group, a carboxyl group, an unsaturated double bond group and an ester bond in its molecule, and the pre-reaction product (A2) is obtained by pre-reacting a mixture containing a polyphenylene ether compound (a2-1) and a compound (a2-2), wherein the polyphenylene ether compound (a2-1) has at least one selected from the group consisting of a hydroxyl group, a carboxyl group and an ester bond in its molecule, and the compound (a2-2) reacts with at least one of the hydroxyl group, the carboxyl group and the ester bond.

3. The resin composition according to claim 2, characterized in that The preliminary reaction product (A2) includes a preliminary reaction product obtained by previously reacting a polyphenylene ether compound having a hydroxyl group in the molecule and an acid anhydride having an acid anhydride group in the molecule.

4. The resin composition according to claim 1, characterized in that The reactive compound (B) includes at least one selected from the group consisting of allyl compounds, acrylate compounds, methacrylate compounds, polybutadiene compounds, styrene compounds, and maleimide compounds.

5. The resin composition according to claim 1, characterized in that The content of the polyphenylene ether compound (A) is 20 to 80 parts by mass based on 100 parts by mass of the total of the polyphenylene ether compound (A) and the reactive compound (B).

6. The resin composition according to claim 1, characterized in that Also contains: Benzoxazine compounds (D).

7. The resin composition according to claim 1, characterized in that The additive (C) includes: at least one of the phosphite antioxidant (C2) and the hindered phenol antioxidant (C3); and the heavy metal deactivator (C1).

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

9. The resin composition according to claim 8, characterized in that The inorganic filler material has been surface treated with a silane coupling agent.

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

11. A film with resin, characterized in that include: A resin layer comprising the resin composition according to any one of claims 1 to 9 or a semi-cured product of the resin composition; as well as Support membrane.

12. A metal foil with resin, characterized in that include: A resin layer comprising the resin composition according to any one of claims 1 to 9 or a semi-cured product of the resin composition; as well as Metal foil.

13. 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 9; and metal foil.

14. A metal foil-clad laminate, characterized in that include: An insulating layer comprising a cured product of the prepreg according to claim 10; as well as Metal foil.

15. A wiring board, characterized in that include: An insulating layer comprising a cured product of the resin composition according to any one of claims 1 to 9; as well as wiring.

16. A wiring board, characterized in that include: An insulating layer comprising a cured product of the prepreg according to claim 10; as well as wiring.

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