Resin composition, cured product, prepreg, metal foil-clad laminate, resin sheet, and printed wiring board

Abstract

Provided are: a resin composition having excellent low water absorption; and a cured product, a prepreg, a metal foil-clad laminate, and a printed wiring board. A resin composition containing a compound (A) represented by formula (M1) and a compound (B) containing two or more carbon-carbon unsaturated double bonds. In formula (M1), A represents a 4-6 membered alicyclic group. # imgabs0 #

Description

[0001] This application is a divisional application of the Chinese patent application with the application date of February 24, 2021, application number 202180016382.5, and invention name "Resin composition, cured product, prepreg, metal foil-clad laminate, resin sheet and printed circuit board". Technical Field

[0002] The present invention relates to a resin composition, a cured product, a prepreg, a metal foil-clad laminate, a resin sheet and a printed circuit board. Background Art

[0003] In recent years, the semiconductors used in communication equipment, communication machines, personal computers, etc. have been highly integrated and miniaturized, and the properties required of printed circuit boards (such as metal foil laminates) used in them have become increasingly stringent. The main properties required include metal foil peel strength, low water absorption, desmear resistance, flame resistance, low dielectric constant, low dielectric loss tangent, low thermal expansion coefficient, heat resistance, etc.

[0004] In order to obtain a printed circuit board with improved properties, resin compositions used as materials for printed circuit boards have been studied. For example, Patent Document 1 discloses a resin composition for a printed circuit board, which comprises: a bifunctional vinylbenzyl compound (a) having a predetermined polyphenylene ether skeleton; a predetermined maleimide compound (b); a predetermined cyanate resin (c); and a predetermined epoxy resin (d).

[0005] Patent Document 2 discloses a resin composition comprising a predetermined cyanate ester compound (A), a predetermined polymaleimide compound (B), and a filler (C) as constituent components.

[0006] Furthermore, Patent Document 3 discloses a resin composition comprising a predetermined polymaleimide compound (A), a modified polyphenylene ether (B) whose terminal is modified with a substituent having a carbon-carbon unsaturated double bond, and a filler (C).

[0007] Prior art literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent Application Publication No. 2010-138364

[0010] Patent Document 2: International Publication No. 2016 / 072404

[0011] Patent Document 3: International Publication No. 2019 / 138992 Summary of the invention

[0012] Problem that the invention aims to solve

[0013] As described above, various resin compositions for printed wiring boards have been studied. In addition, with recent technological innovations, resin compositions that are particularly excellent in low water absorption are sought as one of the demands.

[0014] The present invention aims to solve the above problems, and aims to provide a resin composition having excellent low water absorption, and a cured product, a prepreg, a metal foil-clad laminate, a resin sheet, and a printed circuit board. In particular, the present invention aims to provide a resin composition suitable for printed circuit board applications.

[0015] Solutions for solving problems

[0016] The present inventors have conducted studies based on the above-mentioned problems and have solved the above-mentioned problems by the following means.

[0017] <1> A resin composition comprising: a compound (A) represented by formula (M1) and a compound (B) containing two or more carbon-carbon unsaturated double bonds.

[0018] Formula (M1)

[0019]

[0020] (In formula (M1), R M1 , R M2 , R M3 and R M4 Each independently represents a hydrogen atom or an organic group. M5 and R M6 Each independently represents a hydrogen atom or an alkyl group. M represents a divalent aromatic group. A is a 4- to 6-membered alicyclic group. M7 and R M8 Each is independently an alkyl group. mx is 1 or 2, and lx is 0 or 1. M9 and R M10 Each independently represents a hydrogen atom or an alkyl group. M11 , R M12 , R M13 and R M14 Each independently represents a hydrogen atom or an organic group. nx represents an integer of 1 to 20.

[0021] <2> according to <1> The resin composition, wherein the content of the compound (A) represented by the formula (M1) is 1 to 90 parts by mass based on 100 parts by mass of the resin solid content in the resin composition.

[0022] <3> according to <1> or <2> The resin composition, wherein the content of the compound (B) containing two or more carbon-carbon unsaturated double bonds is 1 to 90 parts by mass, based on 100 parts by mass of the resin solid content in the resin composition.

[0023] <4> according to <1> ~ <3> The resin composition described in any one of the above, further comprising other resin components (C), wherein the other resin components (C) are selected from the group consisting of maleimide compounds other than the compound (A) represented by the aforementioned formula (M1), epoxy compounds, phenolic compounds, oxetane resins, benzoxazine compounds, compounds having polymerizable unsaturated groups other than the aforementioned compound (B) containing two or more carbon-carbon unsaturated double bonds, and one or more cyanate compounds.

[0024] <5> according to <1> ~ <4> The resin composition described above further comprises a filler (D).

[0025] <6> according to <5> The resin composition described above, wherein the content of the filler (D) in the resin composition is 50 to 1600 parts by mass based on 100 parts by mass of the resin solid content.

[0026] <7> according to <1> ~ <6> The resin composition described above, wherein the compound (B) containing two or more carbon-carbon unsaturated double bonds comprises a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds.

[0027] <8> according to <1> ~ <6> The resin composition described in any one of the preceding claims, wherein the compound (B) containing two or more carbon-carbon unsaturated double bonds contains a compound represented by formula (1).

[0028]

[0029] (In formula (1), X represents an aromatic group, -(YO)n2- represents a polyphenylene ether structure, and R 1 , R 2 , and R 3 Each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group, n1 represents an integer of 1 to 6, n2 represents an integer of 1 to 100, and n3 represents an integer of 1 to 4.)

[0030] <9> according to <1> ~ <8> The resin composition described above is used for a printed circuit board.

[0031] <10> A solidified material, which is <1> ~ <9> A cured product of any one of the resin compositions.

[0032] <11> A prepreg, which is composed of a base material and <1> ~ <9> The resin composition described in any one of the above is formed.

[0033] <12> A metal foil-clad laminate comprising: at least one <11> The prepreg; and, a metal foil disposed on one or both sides of the prepreg.

[0034] <13> A resin sheet comprising: a support; and, arranged on the surface of the support <1> ~ <9> A layer formed from any one of the resin compositions.

[0035] <14> A printed circuit board comprises: an insulating layer; and a conductor layer disposed on a surface of the insulating layer.

[0036] The aforementioned insulating layer comprises: <1> ~ <9> A layer formed of the resin composition described in any one of the preceding claims and a layer formed of the resin composition described in any one of the preceding claims <11> At least one of the layers formed by the prepreg.

[0037] Effects of the Invention

[0038] The present invention can provide a resin composition having excellent low water absorption, and a cured product, a prepreg, a metal foil-clad laminate, a resin sheet, and a printed wiring board. In particular, a resin composition suitable for printed wiring board applications can be provided. DETAILED DESCRIPTION

[0039] Hereinafter, a mode for implementing the present invention (hereinafter, simply referred to as "this embodiment") will be described in detail. It should be noted that the following this embodiment is an example for explaining the present invention, and the present invention is not limited to this embodiment.

[0040] In addition, in this specification, "to" is used to mean that the numerical value described before and after it is included as a lower limit and an upper limit.

[0041] In this specification, various physical property values ​​and characteristic values ​​refer to values ​​at 23°C unless otherwise specified.

[0042] In the description of the group (atomic group) in this specification, the description not recorded as substitution and unsubstituted includes the group (atomic group) with a substituent while including the group (atomic group) without a substituent. For example, "alkyl" includes not only the alkyl group without a substituent (unsubstituted alkyl group), but also the alkyl group with a substituent (substituted alkyl group). In this specification, the description not recorded as substitution and unsubstituted is preferably unsubstituted.

[0043] In addition, the "mass part" in this specification refers to the relative amount of a component, and the "mass %" refers to the absolute amount of a component.

[0044] In the present specification, the resin solid content refers to the components other than the filler and the solvent, and mainly includes the compound (A) represented by the formula (M1), the compound (B) containing two or more carbon-carbon unsaturated double bonds, and other resin components (C), elastomers, silane coupling agents, and other components (additives such as flame retardants, etc.) blended as needed.

[0045] The resin composition of the present embodiment is characterized by containing a compound (A) represented by formula (M1) and a compound (B) containing two or more carbon-carbon unsaturated double bonds.

[0046]

[0047] (In formula (M1), R M1 , R M2 , R M3 and R M4 Each independently represents a hydrogen atom or an organic group. M5 and R M6 Each independently represents a hydrogen atom or an alkyl group. M represents a divalent aromatic group. A is a 4- to 6-membered alicyclic group. M7 and R M8 Each is independently an alkyl group. mx is 1 or 2, and lx is 0 or 1. M9 and R M10 Each independently represents a hydrogen atom or an alkyl group. M11 , R M12 , R M13 and R M14 Each independently represents a hydrogen atom or an organic group. nx represents an integer of 1 to 20.

[0048] By using such a resin composition, a cured product of the resin composition having excellent low water absorption can be obtained, and can be preferably used as a material for a printed wiring board.

[0049] The reason why the cured product of the resin composition of the present embodiment has excellent low water absorption is not limited, but it is inferred as described below. That is, it is inferred that: in the present embodiment, by using a compound having two maleimide groups and a fused ring of an alicyclic ring and an aromatic ring such as an indane ring (a compound shown in formula (M1)), a cyclic aliphatic group can be introduced into the cured product, and a cured product of a resin composition having low water absorption and excellent dielectric properties (low dielectric constant (Dk) and / or low dielectric loss tangent (Df)) can be obtained. On the other hand, the aromatic part of the fused ring of an alicyclic ring and an aromatic ring such as the aforementioned indane ring maintains good heat resistance, which improves the possibility of application to printed circuit board applications. Furthermore, by using a compound (B) containing more than two carbon-carbon unsaturated double bonds in combination, the dielectric properties are made good. That is, in the present embodiment, it is valuable in terms of being able to maintain the dielectric properties required for printed circuit boards and being able to achieve low water absorption.

[0050] <Compound (A) represented by formula (M1)>

[0051] The resin composition of the present embodiment contains the compound (A) shown in the formula (M1). The compound shown in the formula (M1) has 2 maleimide groups in 1 molecule, so the compound (A) shown in the formula (M1) reacts with each other, and in addition, the compound (A) shown in the formula (M1) reacts with the compound (B) containing more than 2 carbon-carbon unsaturated double bonds, and then, reacts with other curable resin components (such as "other resin components (C)" described later) to form a cured product, and forms a cured product together with the cured products of the compound (B) containing more than 2 carbon-carbon unsaturated double bonds. In addition, by adopting the compound (A) shown in the formula (M1), the distance between the maleimide groups (the distance between the crosslinking points) becomes appropriate. Therefore, in the resin composition of the present embodiment, the alicyclic ring and the fused ring structure of the aromatic ring such as the indane ring contained in the compound (A) shown in the formula (M1) exist in the cured product with an appropriate distance spacing, and low water absorption can be achieved. Furthermore, by using the compound (A) represented by the formula (M1) in combination with the compound (B) containing two or more carbon-carbon unsaturated double bonds, excellent dielectric properties can be achieved.

[0052] Furthermore, the cured product of the resin composition of the present embodiment comprises the compound (A) shown in the formula (M1), so that the dielectric properties can be well maintained after moisture absorption. Generally, if the cured product of the resin composition absorbs moisture, the dielectric properties deteriorate. However, the part of A of the compound (A) shown in the formula (M1) is an alicyclic structure, so the polarity of the compound becomes low and it is not easy to attract water.

[0053] Hereinafter, the compound represented by formula (M1) will be described.

[0054]

[0055] (In formula (M1), R M1 , R M2 , R M3 and R M4 Each independently represents a hydrogen atom or an organic group. M5 and R M6 Each independently represents a hydrogen atom or an alkyl group. M represents a divalent aromatic group. A is a 4- to 6-membered alicyclic group. M7 and R M8 Each is independently an alkyl group. mx is 1 or 2, and lx is 0 or 1. M9 and R M10 Each independently represents a hydrogen atom or an alkyl group. M11 , R M12 , R M13 and R M14 Each independently represents a hydrogen atom or an organic group. nx represents an integer of 1 to 20.

[0056] R in the formula M1 , R M2 , R M3 and R M4 Each independently represents a hydrogen atom or an organic group. The organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, further preferably an alkyl group having 1 to 6 carbon atoms, further preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group. M1 and R M3 Each independently preferably an alkyl group, R M2 and R M4 A hydrogen atom is preferred.

[0057] R M5 and R M6 Each independently represents a hydrogen atom or an alkyl group, preferably an alkyl group. The alkyl group herein is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, further preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group.

[0058] Ar M Ar represents a divalent aromatic group, preferably phenylene, naphthalene diyl, phenanthrene diyl, anthracene diyl, more preferably phenylene, and still more preferably m-phenylene. M The substituent is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, further preferably an alkyl group having 1 to 6 carbon atoms, further preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group. M Preferably, there is no substitution.

[0059] A is a 4- to 6-membered alicyclic group, more preferably a 5-membered alicyclic group (preferably a group that forms an indane ring together with a benzene ring). M7 and R M8 Each is independently an alkyl group, preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group. mx is 1 or 2, preferably 2. lx is 0 or 1, preferably 1.

[0060] R M9 and R M10 Each independently represents a hydrogen atom or an alkyl group, preferably an alkyl group. The alkyl group herein is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, further preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group.

[0061] R M11 , R M12 , R M13 and R M14 Each independently represents a hydrogen atom or an organic group. The organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, further preferably an alkyl group having 1 to 6 carbon atoms, further preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group. M12 and R M13 Each independently preferably an alkyl group, R M11 and R M14 A hydrogen atom is preferred.

[0062] nx represents an integer of 1 to 20. nx may be an integer of 10 or less.

[0063] It should be noted that the resin composition of the present embodiment may include only one of the compounds (A) shown in the formula (M1) and at least one of the compounds having different values ​​of nx, or may include more than two compounds (A) shown in the formula (M1) and at least one of the compounds having different values ​​of nx. In the case of including more than two kinds, in order to form a low melting point (low softening point), a person having low melt viscosity and excellent operability, the average value (average number of repeating units) n of nx in the compound (A) shown in the formula (M1) in the resin composition is preferably 0.95 or more, more preferably 0.98 or more, further preferably 1.0 or more, and also preferably 1.1 or more, and preferably 10.0 or less, more preferably 8.0 or less, further preferably 7.0 or less, and also preferably 6.0 or less. The same is true for the formula (M2) and formula (M3) described later.

[0064] The compound represented by formula (M1) is preferably a compound represented by the following formula (M2).

[0065]

[0066] (In formula (M2), R M21 , RM22 , R M23 and R M24 Each independently represents a hydrogen atom or an organic group. M25 and R M26 Each independently represents a hydrogen atom or an alkyl group. M27 , R M28 , R M29 and R M30 Each independently represents a hydrogen atom or an organic group. M31 and R M32 Each independently represents a hydrogen atom or an alkyl group. M33 , R M34 , R M35 and R M36 Each independently represents a hydrogen atom or an organic group. M37 , R M38 , R M39 Each independently represents a hydrogen atom or an alkyl group. nx represents an integer of 1 to 20.

[0067] R in the formula M21 , R M22 , R M23 and R M24 Each independently represents a hydrogen atom or an organic group. The organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, further preferably an alkyl group having 1 to 6 carbon atoms, further preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group. M21 and R M23 Preferably, alkyl, R M22 and R M24 A hydrogen atom is preferred.

[0068] R M25 and R M26 Each independently represents a hydrogen atom or an alkyl group, preferably an alkyl group. The alkyl group herein is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, further preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group.

[0069] R M27 , R M28 , R M29 and R M30 Each independently represents a hydrogen atom or an organic group, preferably a hydrogen atom. The organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, further preferably an alkyl group having 1 to 6 carbon atoms, further preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group.

[0070] R M31 and R M32Each independently represents a hydrogen atom or an alkyl group, preferably an alkyl group. The alkyl group herein is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, further preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group.

[0071] R M33 , R M34 , R M35 and R M36 Each independently represents a hydrogen atom or an organic group. The organic group here is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, further preferably an alkyl group having 1 to 6 carbon atoms, further preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group.

[0072] R M33 and R M36 Preferably, a hydrogen atom, R M34 and R M35 An alkyl group is preferred.

[0073] R M37 , R M38 , R M39 Each independently represents a hydrogen atom or an alkyl group, preferably an alkyl group. The alkyl group herein is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, further preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group.

[0074] nx represents an integer of 1 to 20. nx may be an integer of 10 or less.

[0075] The compound represented by formula (M2) is preferably a compound represented by the following formula (M3).

[0076]

[0077] (In formula (M3), nx represents an integer of 1 to 20.)

[0078] nx may be an integer less than 10.

[0079] The molecular weight of the compound (A) shown in formula (M1) is preferably 500 or more, more preferably 600 or more, and further preferably 700 or more. By setting it to above the aforementioned lower limit, the dielectric properties (low dielectric properties) and low water absorption of the obtained cured product tend to be further improved. In addition, the molecular weight of the compound (A) shown in formula (M1) is preferably 10000 or less, more preferably 9000 or less, further preferably 7000 or less, further preferably 5000 or less, and further preferably 4000 or less. By setting it to below the aforementioned upper limit, the heat resistance and workability of the cured product tend to be further improved.

[0080] In addition, the compound (A) shown in the formula (M1) used in the present embodiment preferably has excellent dielectric properties of its cured product. For example, for the cured product of the compound (A) shown in the formula (M1) used in the present embodiment, the dielectric constant (Dk) measured by the resonant cavity perturbation method is preferably 3.0 or less, more preferably 2.6 or less. In addition, the lower limit of the aforementioned dielectric constant is, for example, actually more than 2.0. In addition, for the cured product of the compound (A) shown in the formula (M1) used in the present embodiment, the dielectric loss tangent (Df) measured by the resonant cavity perturbation method is preferably 0.01 or less, more preferably 0.007 or less. In addition, the lower limit of the aforementioned dielectric loss tangent is, for example, actually more than 0.0001.

[0081] In addition, the compound (A) represented by the formula (M1) used in the present embodiment preferably has a high heat resistance of its cured product. For the cured product of the compound (A) represented by the formula (M1) used in the present embodiment, the glass transition temperature measured according to the JIS C6481:1996 dynamic viscoelasticity measurement is preferably 180°C or more, more preferably 200°C or more, and further preferably 230°C or more. By setting it to above the aforementioned lower limit, a cured product with better heat resistance can be obtained. In addition, the upper limit of the aforementioned glass transition temperature is actually below 400°C.

[0082] As the compound (A) represented by the formula (M1) used in the present embodiment, for example, X9-450 and X9-470 manufactured by DIC Corporation can be used.

[0083] For the resin composition of the present embodiment, when the resin solid content in the resin composition is set to 100 parts by mass, the content of the compound (A) shown in the above formula (M1) is preferably 1 to 90 parts by mass. For the lower limit of the content of the compound (A) shown in formula (M1), when the resin solid content in the resin composition is set to 100 parts by mass, it is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, further preferably 20 parts by mass or more, also preferably 30 parts by mass or more, and further preferably 40 parts by mass or more, and it can also be 60 parts by mass or more, 70 parts by mass or more. By setting it to above the above lower limit, there is a tendency that the heat resistance of the obtained cured product is further improved. In addition, for the upper limit of the content of the compound (A) shown in formula (M1), when the resin solid content in the resin composition is set to 100 parts by mass, it is preferably 88 parts by mass or less, more preferably 85 parts by mass or less, further preferably 83 parts by mass or less, also preferably 80 parts by mass or less, and it can also be 79 parts by mass or less. By setting it to below the above upper limit, there is a tendency that the low water absorption of the obtained cured product is further improved.

[0084] In addition, for the resin composition of the present embodiment, relative to the total amount of resin solids, the content of the compound (A) shown in the formula (M1) is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, also preferably 30% by mass or more, and further preferably 40% by mass or more, and may be 60% by mass or more, 70% by mass or more. By being set to above the lower limit, there is a tendency that the heat resistance of the obtained cured product is further improved. In addition, the upper limit of the content of the compound (A) shown in the formula (M1) is preferably 88% by mass or less of the resin solids in the resin composition, more preferably 85% by mass or less, further preferably 83% by mass or less, also preferably 80% by mass or less, and may be 79% by mass or less. By being set to below the upper limit, there is a tendency that the low water absorption of the cured product obtained is further improved.

[0085] The resin composition of the present embodiment may contain only one compound (A) represented by the formula (M1), or may contain two or more compounds (A) represented by the formula (M1). When containing two or more compounds (A), the total amount is preferably within the above range.

[0086] <Compound containing two or more carbon-carbon unsaturated double bonds (B)>

[0087] The resin composition of the present embodiment contains: a compound (B) containing two or more carbon-carbon unsaturated double bonds. In the present embodiment, by combining the compound (A) shown in formula (M1) with the compound (B) containing two or more carbon-carbon unsaturated double bonds, it is possible to achieve better dielectric properties than the case of combining the maleimide compound used so far with the compound (B) containing two or more carbon-carbon unsaturated double bonds.

[0088] The carbon-carbon unsaturated double bond contained in the compound (B) containing two or more carbon-carbon unsaturated double bonds used in the present embodiment is an unsaturated group that can be polymerized, and is usually a carbon-carbon unsaturated double bond that reacts with any reactive functional group. The compound (B) containing two or more carbon-carbon unsaturated double bonds is, for example, a compound containing a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, etc.

[0089] As the compound (B) containing two or more carbon-carbon unsaturated double bonds used in the present embodiment, a wide range of compounds containing two or more carbon-carbon unsaturated double bonds generally used in printed wiring boards can be used.

[0090] Specifically, the upper limit of the number of carbon-carbon unsaturated double bonds of the compound (B) containing two or more carbon-carbon unsaturated double bonds used in the present embodiment is preferably 10 or less, more preferably 5 or less, and further preferably 2. By setting it below the above upper limit, there is a tendency that the heat resistance of the obtained cured product and the operability of the resin composition are further improved.

[0091] In addition, the compound (B) containing more than two carbon-carbon unsaturated double bonds used in the present embodiment preferably has excellent dielectric properties of its cured product. For example, the dielectric constant (Dk) of the cured product of the compound (B) containing more than two carbon-carbon unsaturated double bonds used in the present embodiment measured by the resonant cavity perturbation method is preferably 3.0 or less, more preferably 2.6 or less. In addition, the lower limit of the aforementioned dielectric constant is, for example, actually more than 2.0. In addition, the dielectric loss tangent (Df) of the cured product of the compound (B) containing more than two carbon-carbon unsaturated double bonds used in the present embodiment measured by the resonant cavity perturbation method is preferably 0.01 or less, more preferably 0.007 or less. In addition, the lower limit of the aforementioned dielectric loss tangent is, for example, actually more than 0.0001.

[0092] In addition, the compound (B) containing two or more carbon-carbon unsaturated double bonds used in the present embodiment preferably has high heat resistance of its cured product. The glass transition temperature of the cured product of the compound (B) containing two or more carbon-carbon unsaturated double bonds used in the present embodiment measured according to JIS C6481 dynamic viscoelasticity measurement is preferably 150°C or more, more preferably 180°C or more, and further preferably 200°C or more. By setting it to above the above lower limit, a cured product with excellent heat resistance can be obtained. In addition, the upper limit of the above glass transition temperature is actually below 400°C.

[0093] The number average molecular weight of the compound (B) containing more than two carbon-carbon unsaturated double bonds based on the polystyrene conversion of the GPC method is preferably 500 or more, more preferably 1000 or more, further preferably 1200 or more, also preferably 1500 or more, and may be 1800 or more. By setting it to more than the aforementioned lower limit, there is a tendency that the low dielectric of the obtained cured product is further improved. In addition, the number average molecular weight of the compound (B) containing more than two carbon-carbon unsaturated double bonds is preferably 7000 or less, more preferably 5000 or less, further preferably 3500 or less, also preferably 3000 or less, and further preferably 2300 or less. By setting it to less than the aforementioned upper limit, there is a tendency that the heat resistance of the cured product obtained is further improved.

[0094] The compound (B) containing two or more carbon-carbon unsaturated double bonds used in the present embodiment preferably contains: a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds. Furthermore, preferably, more than 90% by mass (more preferably more than 95% by mass, further preferably more than 99% by mass) of the compound (B) containing two or more carbon-carbon unsaturated double bonds contained in the resin composition of the present embodiment is a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds.

[0095] The polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds is preferably a polyphenylene ether compound containing two or more vinylbenzyl groups.

[0096] The following describes these details.

[0097] Examples of the polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds include compounds having a phenylene ether skeleton represented by the following formula (X1).

[0098]

[0099] (In formula (X1), R 24 , R 25 , R 26 and R 27 are optionally the same or different and represent an alkyl group, an aryl group, a halogen atom or a hydrogen atom having 6 or less carbon atoms.

[0100] The polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds may further contain: Formula (X2):

[0101]

[0102] (In formula (X2), R 28 , R 29 , R 30 , R 34 and R 35 R may be the same or different and represents an alkyl group with a carbon number of 6 or less or a phenyl group. 31 , R 32 and R 33 Optionally the same or different, and are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.)

[0103] The repeating unit and / or formula (X3) shown:

[0104]

[0105] (In formula (X3), R 36 , R 37 , R 38 , R 39 , R 40 , R41 , R 42 and R 43 are the same or different and are hydrogen atoms, alkyl groups having 6 or less carbon atoms, or phenyl groups. -A- is a linear, branched, or cyclic divalent hydrocarbon group having 20 or less carbon atoms. ) is a repeating unit.

[0106] The polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds is preferably a modified polyphenylene ether compound (hereinafter, sometimes referred to as "modified polyphenylene ether compound (g)") in which a part or all of the terminal is functionalized with an ethylenically unsaturated group, and more preferably a modified polyphenylene ether compound having a vinyl benzyl group at the terminal. By adopting such a modified polyphenylene ether compound (g), the dielectric loss tangent (Df) of the cured product of the resin composition can be further reduced, and the metal foil peel strength can be improved. These can be used alone or in combination of two or more.

[0107] The manufacturing method of the modified polyphenylene ether compound is not particularly limited as long as the effect of the present invention can be obtained. For example, a substance functionalized with an ethylenically unsaturated group (specifically, vinylbenzyl, etc.) can be manufactured as follows: a bifunctional phenylene ether oligomer and vinylbenzyl chloride are dissolved in a solvent, a base is added under heating and stirring to react, and the resin is solidified, thereby manufacturing. A substance functionalized with a carboxyl group can be manufactured, for example, as follows: in the presence or absence of a free radical initiator, a polyphenylene ether compound and an unsaturated carboxylic acid, or a functionalized derivative thereof are melt-kneaded and reacted, thereby manufacturing. Alternatively, it can also be manufactured as follows: a polyphenylene ether compound and an unsaturated carboxylic acid, or a functional group derivative thereof are dissolved in an organic solvent in the presence or absence of a free radical initiator, and reacted in a solution, thereby manufacturing.

[0108] The ethylenically unsaturated group contained in the modified polyphenylene ether compound (g) can enumerate the alkenyl aryls such as vinyl, allyl, acryloyl, methacryloyl, acryl, butenyl, hexenyl and octenyl, cyclic alkenyls such as cyclopentenyl and cyclohexenyl, vinylbenzyl and vinylnaphthyl, preferably vinylbenzyl. When the modified polyphenylene ether compound (g) has more than 2 ethylenically unsaturated groups, the more than 2 ethylenically unsaturated groups present can be the same functional group, or different functional groups. By adopting this modified polyphenylene ether compound, the dielectric loss tangent (Df) of the cured product of resin combination can be further reduced, and the metal foil peel strength is improved.

[0109] Examples of the modified polyphenylene ether compound (g) include compounds represented by formula (1).

[0110]

[0111] (In formula (1), X represents an aromatic group, -(YO)n2- represents a polyphenylene ether structure, and R 1 , R 2 and R 3 Each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group, n1 represents an integer of 1 to 6, n2 represents an integer of 1 to 100, and n3 represents an integer of 1 to 4.)

[0112] When n2 and / or n3 are integers greater than 2, n2 structural units (YO) and / or n3 structural units may be the same or different. n3 is preferably 2 or greater, more preferably 2.

[0113] The modified polyphenylene ether compound (g) in the present embodiment is preferably represented by formula (2).

[0114]

[0115] Here, -(OXO)- is preferably represented by formula (3):

[0116]

[0117] (In formula (3), R 4 , R 5 , R 6 , R 10 and R 11 R may be the same or different and is an alkyl group with a carbon number of 6 or less or a phenyl group. 7 , R 8 and R 9 Optionally the same or different, and are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.)

[0118] And / or formula (4):

[0119]

[0120] (In formula (4), R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 and R 19 are optionally the same or different and are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. -A- is a linear, branched, or cyclic divalent hydrocarbon group having 20 or less carbon atoms. ) represents.

[0121] In addition, -(YO)- is preferably represented by formula (5):

[0122]

[0123] (In formula (5), R 20 , R 21 R may be the same or different and is an alkyl group with a carbon number of 6 or less or a phenyl group. 22 , R 23 They are optionally the same or different and are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.

[0124] In formula (2), at least one of a and b represents an integer of 0 to 100 other than 0, preferably an integer of 0 to 50 other than 0, and more preferably an integer of 1 to 30. When a and / or b is an integer of 2 or more, two or more -(YO)- groups are each independently arranged in one structure, or two or more structures are arranged in blocks or randomly.

[0125] Examples of -A- in formula (4) include, but are not limited to, divalent organic groups such as methylene, ethylidene, 1-methylethylidene, 1,1-propylidene, 1,4-phenylenebis(1-methylethylidene) group, 1,3-phenylenebis(1-methylethylidene) group, cyclohexylidene, phenylmethylene, naphthylmethylene, and 1-phenylethylidene.

[0126] Among the above-mentioned modified polyphenylene ether compounds (g), R 4 , R 5 , R 6 , R 10 , R 11 , R 20 and R 21 is an alkyl group with a carbon number of 3 or less, R 7 , R 8 , R 9 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 22 and R 23 The polyphenylene ether compound is a hydrogen atom or an alkyl group having 3 or less carbon atoms, and it is particularly preferred that -(OXO)- represented by formula (3) or (4) is formula (9), formula (10) and / or formula (11), and -(YO)- represented by formula (5) is formula (12) or formula (13). When a and / or b is an integer greater than 2, two or more -(YO)- are each independently a structure in which two or more of formula (12) and / or formula (13) are arranged, or a structure in which formula (12) and formula (13) are arranged in blocks or randomly.

[0127]

[0128] (In formula (10), R 44 , R 45 , R 46 and R 47 are the same or different and are hydrogen or methyl. -B- is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.

[0129] As specific examples of -B-, the same ones as the specific examples of -A- in formula (4) can be given.

[0130]

[0131] (In formula (11), -B- is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.)

[0132] As specific examples of -B-, the same ones as the specific examples of -A- in formula (4) can be given.

[0133]

[0134] The preparation method (manufacturing method) of the modified polyphenylene ether compound (g) represented by formula (2) is not particularly limited, and it can be manufactured, for example, by the following steps: a step of subjecting a bifunctional phenol compound and a monofunctional phenol compound to oxidative coupling to obtain a bifunctional phenylene ether oligomer (oxidative coupling step); and a step of subjecting the terminal phenolic hydroxyl group of the obtained bifunctional phenylene ether oligomer to vinyl benzyl etherification (vinyl benzyl etherification step). In addition, as such a modified polyphenylene ether compound, for example, the one manufactured by Mitsubishi Gas Chemical Co., Ltd. (OPE-2St1200, etc.) can be used.

[0135] In the oxidative coupling step, for example, a bifunctional phenol compound, a monofunctional phenol compound and a catalyst are dissolved in a solvent, and oxygen is blown into the solvent under heating and stirring to obtain a bifunctional phenylene ether oligomer. The bifunctional phenol compound is not particularly limited, and examples thereof include at least one selected from the group consisting of 2,2',3,3',5,5'-hexamethyl-(1,1'-biphenol)-4,4'-diol, 4,4'-methylenebis(2,6-dimethylphenol), 4,4'-dihydroxyphenylmethane, and 4,4'-dihydroxy-2,2'-diphenylpropane. The monofunctional phenol compound is not particularly limited, and examples thereof include 2,6-dimethylphenol and / or 2,3,6-trimethylphenol. The catalyst is not particularly limited, and examples thereof include copper salts (e.g., CuCl, CuBr, CuI, CuCl2, CuBr2, etc.), amines (e.g., di-n-butylamine, n-butyldimethylamine, N,N'-di-tert-butylethylenediamine, pyridine, N,N,N',N'-tetramethylethylenediamine, piperidine, imidazole, etc.), etc. The solvent is not particularly limited, and examples thereof include at least one selected from the group consisting of toluene, methanol, methyl ethyl ketone, and xylene.

[0136] In the vinylbenzyl etherification step, for example, it can be manufactured as follows: the bifunctional phenyl ether oligomer obtained by the oxidative coupling step and vinylbenzyl chloride are dissolved in a solvent, a base is added under heating and stirring to react, and the resin is solidified, thereby manufacturing. As vinylbenzyl chloride, there is no particular limitation, and for example, at least one selected from the group consisting of o-vinylbenzyl chloride, m-vinylbenzyl chloride, and p-vinylbenzyl chloride can be cited. As the base, there is no particular limitation, and for example, at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium methoxide and sodium ethoxide can be cited. In the vinylbenzyl etherification step, an acid can also be used to neutralize the base remaining after the reaction. As the acid, there is no particular limitation, and for example, at least one selected from the group consisting of hydrochloric acid, sulfuric acid, phosphoric acid, boric acid and nitric acid can be cited. As the solvent, there is no particular limitation, and for example, at least one selected from the group consisting of toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, dichloromethane and chloroform can be cited. Examples of methods for solidifying the resin include a method of evaporating the solvent to dry the resin, a method of mixing the reaction solution with a poor solvent to reprecipitate the mixture, and the like.

[0137] In addition to the above, the polyphenylene ether compound used in the present embodiment may also be an unmodified polyphenylene ether compound having a hydroxyl group at the end. As the unmodified polyphenylene ether compound, for example, the descriptions in paragraphs 0011 to 0016 of Japanese Patent Application Publication No. 2017-119739 may be adopted, and these contents are incorporated into this specification.

[0138] The polyphenylene ether compound (preferably modified polyphenylene ether compound (g)) containing two or more carbon-carbon unsaturated double bonds preferably has a number average molecular weight based on polystyrene conversion by GPC (gel permeation chromatography) method of 500 or more and 3000 or less. By having a number average molecular weight of 500 or more, there is a tendency to further suppress the tackiness of the resin composition of the present embodiment when forming a coating film. By having a number average molecular weight of 3000 or less, there is a tendency to further improve the solubility in solvents.

[0139] In addition, the polyphenylene ether compound (preferably the modified polyphenylene ether compound (g)) containing two or more carbon-carbon unsaturated double bonds has a polystyrene-equivalent weight average molecular weight based on GPC of preferably 800 to 10000, more preferably 800 to 5000. By setting it to be above the above lower limit, the dielectric constant (Dk) and dielectric loss tangent (Df) of the cured product of the resin composition tend to be lower, and by setting it to be below the above upper limit, the solubility of the resin composition in the solvent, low viscosity and moldability when it is made into a varnish described later tend to be further improved.

[0140] Furthermore, when it is a modified polyphenylene ether compound (g), the terminal carbon-carbon unsaturated double bond equivalent is preferably 400 to 5000g, more preferably 400 to 2500g relative to each carbon-carbon unsaturated double bond. By setting it above the above lower limit, the dielectric constant (Dk) and dielectric loss tangent (Df) of the cured product of the resin composition tend to become lower. By setting it below the above upper limit, the solubility of the resin composition in the solvent, low viscosity and moldability tend to be further improved.

[0141] For the resin composition of the present embodiment, when the resin solid content in the resin composition is set to 100 parts by mass, the content of the compound (B) comprising more than 2 carbon-carbon unsaturated double bonds is preferably 1 to 90 parts by mass. For the lower limit of the content of the compound (B) comprising more than 2 carbon-carbon unsaturated double bonds, when the resin solid content in the resin composition is set to 100 parts by mass, preferably more than 3 parts by mass, more preferably more than 7 parts by mass, further preferably more than 12 parts by mass, also preferably more than 15 parts by mass, and further preferably more than 18 parts by mass. By being set to more than the aforementioned lower limit, there is a tendency for the low water absorption and dielectric properties (Dk and / or Df) of the obtained cured product to be further improved. In addition, for the upper limit of the content of the compound (B) comprising more than 2 carbon-carbon unsaturated double bonds, when the resin solids content in the resin combination is set to 100 mass parts, preferably below 80 mass parts, more preferably below 70 mass parts, further preferably below 60 mass parts, also preferably below 50 mass parts, and then also preferably below 40 mass parts, can also be below 30 mass parts, below 25 mass parts.By being set to below the aforementioned upper limit, there is a tendency that the heat resistance and chemical resistance of the cured product obtained are further improved.

[0142] In addition, for the resin composition of the present embodiment, the content of the compound (B) comprising more than 2 carbon-carbon unsaturated double bonds is preferably more than 3% by mass of resin solids, more preferably more than 7% by mass, further preferably more than 12% by mass, also preferably more than 15% by mass, and further preferably more than 18% by mass. By being set to more than the lower limit, there is a tendency that the low water absorption and dielectric properties (Dk and / or Df) of the cured product obtained are further improved. Moreover, the upper limit of the content of the compound (B) comprising more than 2 carbon-carbon unsaturated double bonds is preferably less than 80% by mass of the resin solids in the resin composition, more preferably less than 70% by mass, further preferably less than 60% by mass, also preferably less than 50% by mass, and further preferably less than 40% by mass, and can also be less than 30% by mass, less than 25% by mass. By being set to less than the aforementioned upper limit, there is a tendency that the heat resistance and chemical resistance of the cured product obtained are further improved.

[0143] The resin composition of the present embodiment may contain only one compound (B) containing two or more carbon-carbon unsaturated double bonds, or may contain two or more compounds (B) containing two or more carbon-carbon unsaturated double bonds. When containing two or more compounds, the total amount is preferably within the above range.

[0144] For the resin composition of the present embodiment, the total amount of the compound (A) shown in the formula (M1) and the compound (B) comprising more than 2 carbon-carbon unsaturated double bonds is preferably more than 20% by mass of the resin solid component, more preferably more than 30% by mass, further preferably more than 40% by mass, also preferably more than 50% by mass, and further preferably more than 60% by mass, further preferably more than 70% by mass, and can also be more than 80% by mass, more than 90% by mass, more than 95% by mass. By being set to more than the aforementioned lower limit, there is a tendency that the heat resistance, low water absorption and dielectric properties of the cured product obtained are further improved. In addition, the upper limit of the aforementioned total amount is preferably less than 99.9% by mass of the resin solid component in the resin composition, more preferably less than 99% by mass. By being set to less than the aforementioned upper limit, there is a tendency that the heat resistance, low water absorption and dielectric properties of the cured product obtained are further improved.

[0145] In the resin composition of the present embodiment, the mass ratio of the compound (A) represented by the formula (M1) to the compound (B) containing two or more carbon-carbon unsaturated double bonds is preferably 9: 1 to 1: 9, more preferably 5: 1 to 1: 3, further preferably 4.5: 1 to 1.5: 1, and still more preferably 4: 1 to 2: 1. If such a blending ratio is set, the fused ring of the alicyclic ring and the aromatic ring such as the indane ring contained in the compound (A) represented by the formula (M1) is present in the cured product at an appropriate distance spacing, and the low water absorption can be relatively improved.

[0146] <Other resin components (C)>

[0147] The resin composition of the present embodiment may further include: one or more other resin components (C) selected from the group consisting of maleimide compounds, epoxy compounds, phenolic compounds, oxetane resins, benzoxazine compounds, compounds with polymerizable unsaturated groups other than compounds (B) containing more than two carbon-carbon unsaturated double bonds, and cyanate compounds, preferably including one or more other components selected from the group consisting of maleimide compounds, epoxy compounds, phenolic compounds, oxetane resins, benzoxazine compounds, and compounds with polymerizable unsaturated groups other than compounds (B) containing more than two carbon-carbon unsaturated double bonds other than compounds (A) shown in formula (M1). By including such a component, other desired properties required by the printed circuit board can be more effectively exerted. In the present embodiment, it is particularly preferred to include maleimide compounds and epoxy compounds, and more preferably to include epoxy compounds.

[0148] The above-mentioned other resin components (C) are preferably cured with excellent dielectric properties. For example, the dielectric constant (Dk) of the other resin components (C) is preferably 4.0 or less, more preferably 3.5 or less, as measured by the resonant cavity perturbation method. In addition, the lower limit of the aforementioned dielectric constant (Dk) is, for example, actually greater than 2.0. In addition, the dielectric loss tangent (Df) of the other resin components (C) is preferably 0.03 or less, more preferably 0.002 or less, as measured by the resonant cavity perturbation method. In addition, the lower limit of the aforementioned dielectric loss tangent (Df) is, for example, actually greater than 0.0001.

[0149] In addition, the other resin component (C) preferably has a high heat resistance in its cured product. For example, the other resin component (C) preferably has a cured product having a glass transition temperature of 150°C or more, more preferably 180°C or more, and further preferably 200°C or more, as measured by the dynamic viscoelasticity measurement according to JIS C6481. By setting it to be above the above lower limit, a cured product with better heat resistance can be obtained. In addition, the upper limit of the above glass transition temperature is actually below 400°C.

[0150] In addition, the resin composition of the present embodiment may include an elastomer. Furthermore, the resin composition of the present embodiment may include a silane coupling agent. Furthermore, the resin composition of the present embodiment may include an active ester compound. Furthermore, additives commonly used in the technical field of the present invention may be included within the scope of not departing from the gist of the present invention.

[0151] Hereinafter, details of other resin components (C), the elastomer, the silane coupling agent, and the active ester will be described.

[0152] <<Maleimide compounds other than the compound (A) represented by the formula (M1)>>

[0153] The resin composition of the present embodiment may contain a maleimide compound other than the compound (A) represented by the formula (M1) (hereinafter, sometimes simply referred to as “other maleimide compound”).

[0154] The other maleimide compounds are not particularly limited as long as they are compounds having one or more (preferably 2 to 12, more preferably 2 to 6, further preferably 2 to 4, further preferably 2 or 3, and further preferably 2) maleimide groups in one molecule, and a wide range of compounds commonly used in the field of printed wiring boards can be used.

[0155] Examples of other maleimide compounds include compounds represented by formula (2M) to formula (4M). When these other maleimide compounds are used in printed wiring board materials (eg, laminates, metal foil-clad laminates), etc., excellent heat resistance can be imparted.

[0156]

[0157] In formula (2M), R 54 Each independently represents a hydrogen atom or a methyl group, and n4 represents an integer greater than 1. n4 is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, further preferably an integer of 1 to 3, and still more preferably 1 or 2.

[0158]

[0159] In formula (3M), R 55 Each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group; and n5 represents an integer of 1 to 10.

[0160] R 55 Preferred are hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, and phenyl group, more preferably one of hydrogen atom and methyl group, and further preferably hydrogen atom. n5 is preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and further preferably 1 or 2.

[0161]

[0162] In formula (4M), R 56 Each independently represents a hydrogen atom, a methyl group or an ethyl group, and R 57 Each independently represents a hydrogen atom or a methyl group.

[0163] Among the compounds represented by the aforementioned formula (2M) to formula (4M), the compound represented by formula (3M) is more preferable.

[0164] Other maleimide compounds can be prepared by known methods, or commercial products can be used. For commercial products, for example, as the compound represented by formula (3M), "MIR-3000" manufactured by Nippon Kayaku Co., Ltd. can be cited, as the compound represented by formula (2M), "BMI-2300" manufactured by Yamato Chemical Industry Co., Ltd. can be cited, and as the compound represented by formula (4M), "BMI-70" manufactured by KI Chemical Industry Co., Ltd. can be cited.

[0165] In addition, other maleimide compounds other than the above include, for example, oligomers of phenylmethane maleimide, m-phenylene bismaleimide, 2,2-bis(4-(4-maleimidephenoxy)-phenyl)propane, 4-methyl-1,3-phenylene bismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenyl sulfone bismaleimide, 1,3-bis(3-maleimidephenoxy)benzene, 1,3-bis(4-maleimidephenoxy)benzene, and prepolymers thereof, and prepolymers of these maleimides and amines.

[0166] For the lower limit of the content of other maleimide compounds, when the resin composition of the present embodiment includes other maleimide compounds, relative to 100 parts by mass of the resin solids in the resin composition, preferably more than 1 part by mass, more preferably more than 10 parts by mass, can be more than 15 parts by mass. By the content of other maleimide compounds being more than 1 part by mass, there is a tendency for the flame retardancy of the obtained cured product to be improved. In addition, for the upper limit of the content of other maleimide compounds, when the resin composition of the present embodiment includes other maleimide compounds, relative to 100 parts by mass of the resin solids in the resin composition, preferably less than 70 parts by mass, more preferably less than 50 parts by mass, further preferably less than 30 parts by mass, also preferably less than 20 parts by mass. By the content of other maleimide compounds being less than 70 parts by mass, there is a tendency for metal foil peel strength and low water absorption to be improved.

[0167] The resin composition in the present embodiment may contain only one other maleimide compound, or may contain two or more other maleimide compounds. When containing two or more other maleimide compounds, the total amount is preferably within the above range.

[0168] The resin composition in the present embodiment may be configured to contain substantially no other maleimide compound. Substantially containing no other maleimide compound means that the content of the other maleimide compound is less than 1 part by mass based on 100 parts by mass of the resin solid content in the resin composition.

[0169] <<Epoxy compounds>>

[0170] The resin composition of the present embodiment may contain an epoxy compound.

[0171] The epoxy compound is not particularly limited as long as it is a compound or resin having one or more (preferably 2 to 12, more preferably 2 to 6, further preferably 2 to 4, further preferably 2 or 3, and further preferably 2) epoxy groups in one molecule, and a wide range of compounds commonly used in the field of printed wiring boards can be used.

[0172] Examples of the epoxy compound include bisphenol A epoxy resin, bisphenol E epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, bisphenol A novolac epoxy resin, glycidyl ester epoxy resin, aralkyl novolac epoxy resin, biphenyl aralkyl epoxy resin, naphthyl ether epoxy resin, cresol novolac epoxy resin, polyfunctional phenol epoxy resin, naphthalene epoxy resin, anthracene epoxy resin, naphthalene skeleton modified novolac epoxy resin, phenol aralkyl epoxy resin, naphthol aralkyl epoxy resin, dicyclopentadiene epoxy resin, biphenyl epoxy resin, alicyclic epoxy resin, polyol epoxy resin, phosphorus-containing epoxy resin, compounds obtained by epoxidizing double bonds of glycidylamine, glycidyl ester, butadiene, etc., compounds obtained by reacting hydroxyl-containing silicone resins with epichlorohydrin, and the like. By using these, the moldability and adhesion of the resin composition are improved. Among these, biphenyl aralkyl type epoxy resins, naphthyl ether type epoxy resins, multifunctional phenol type epoxy resins, and naphthalene type epoxy resins are preferred from the viewpoint of further improving flame retardancy and heat resistance, and biphenyl aralkyl type epoxy resins are more preferred.

[0173] The resin composition of the present embodiment preferably includes an epoxy compound within the range that does not damage the effect of the present invention. In the case where the resin composition of the present embodiment includes an epoxy compound, its content is relative to 100 parts by mass of the resin solid component in the resin composition, preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and further preferably 2 parts by mass or more. By the content of the epoxy compound being more than 0.1 parts by mass, there is a tendency for metal foil peel strength and toughness to improve. For the upper limit of the content of the epoxy compound, in the case where the resin composition of the present embodiment includes an epoxy compound, relative to 100 parts by mass of the resin solid component in the resin composition, preferably less than 50 parts by mass, more preferably less than 30 parts by mass, further preferably less than 20 parts by mass, further preferably less than 10 parts by mass, and further preferably less than 8 parts by mass, and further preferably less than 5 parts by mass. By the content of the epoxy compound being less than 50 parts by mass, there is a tendency for the electrical properties of the obtained cured product to improve.

[0174] The resin composition in the present embodiment may contain only one epoxy compound or two or more epoxy compounds. When containing two or more epoxy compounds, the total amount is preferably within the above range.

[0175] <<Phenol compounds>>

[0176] The resin composition of the present embodiment may contain a phenol compound.

[0177] The phenol compound is not particularly limited as long as it has one or more (preferably 2 to 12, more preferably 2 to 6, further preferably 2 to 4, further preferably 2 or 3, and further preferably 2) phenolic hydroxyl groups in one molecule, and a wide range of compounds commonly used in the field of printed wiring boards can be used.

[0178] Examples of the phenolic compound include bisphenol A type phenolic resin, bisphenol E type phenolic resin, bisphenol F type phenolic resin, bisphenol S type phenolic resin, phenol novolac resin, bisphenol A novolac type phenolic resin, glycidyl ester type phenolic resin, aralkyl novolac phenolic resin, biphenyl aralkyl type phenolic resin, cresol novolac type phenolic resin, multifunctional phenolic resin, naphthol resin, naphthol novolac resin, multifunctional naphthol resin, anthracene type phenolic resin, naphthalene skeleton modified novolac type phenolic resin, phenol aralkyl type phenolic resin, naphthol aralkyl type phenolic resin, dicyclopentadiene type phenolic resin, biphenyl type phenolic resin, alicyclic phenolic resin, polyol type phenolic resin, phosphorus-containing phenolic resin, hydroxyl-containing silicone resin, and the like. Among these, at least one selected from the group consisting of biphenyl aralkyl phenol resins, naphthol aralkyl phenol resins, phosphorus-containing phenol resins, and hydroxyl-containing silicone resins is preferred from the viewpoint of further improving the flame retardancy of the obtained cured product.

[0179] The resin composition of the present embodiment preferably contains a phenol compound within a range that does not impair the effects of the present invention. When the resin composition of the present embodiment contains a phenol compound, its content is preferably 0.1 parts by mass or more, and preferably 50 parts by mass or less relative to 100 parts by mass of the resin solid content in the resin composition.

[0180] The resin composition in the present embodiment may contain only one phenol compound or two or more phenol compounds. When containing two or more phenol compounds, the total amount is preferably within the above range.

[0181] The resin composition in the present embodiment may be configured to contain substantially no phenol compound. Substantially containing no phenol compound means that the content of the phenol compound is less than 0.1 parts by mass based on 100 parts by mass of the resin solid content in the resin composition.

[0182] <<Oxetane resin>>

[0183] The resin composition of the present embodiment may contain an oxetane resin.

[0184] The oxetane resin is not particularly limited as long as it is a compound having one or more (preferably 2 to 12, more preferably 2 to 6, further preferably 2 to 4, further preferably 2 or 3, further preferably 2) oxetane groups, and a wide range of compounds commonly used in the field of printed wiring boards can be used.

[0185] Examples of the oxetane resin include oxetane, alkyloxetane (e.g., 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3,3-dimethyloxetane, etc.), 3-methyl-3-methoxymethyloxetane, 3,3-bis(trifluoromethyl)oxetane, 2-chloromethyloxetane, 3,3-bis(chloromethyl)oxetane, biphenyl-type oxetane, OXT-101 (manufactured by Toagosei Co., Ltd.), and OXT-121 (manufactured by Toagosei Co., Ltd.).

[0186] The resin composition of the present embodiment preferably includes an oxetane resin within the range of not damaging the effect of the present invention. In the case where the resin composition of the present embodiment includes an oxetane resin, its content is relative to 100 parts by mass of the resin solids in the resin composition, preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and further preferably 2 parts by mass or more. By the content of the oxetane resin being more than 0.1 parts by mass, there is a tendency for the metal foil peel strength and toughness to improve. For the upper limit of the content of the oxetane resin, in the case where the resin composition of the present embodiment includes an oxetane resin, relative to 100 parts by mass of the resin solids in the resin composition, preferably less than 50 parts by mass, more preferably less than 30 parts by mass, further preferably less than 20 parts by mass, also preferably less than 10 parts by mass, and further preferably less than 8 parts by mass. By the content of the oxetane resin being less than 50 parts by mass, there is a tendency for the electrical properties of the cured product obtained to improve.

[0187] The resin composition in the present embodiment may contain only one oxetane resin or two or more oxetane resins. When containing two or more oxetane resins, the total amount is preferably within the above range.

[0188] The resin composition in the present embodiment may be configured to contain substantially no oxetane resin. Substantially containing no oxetane resin means that the content of the oxetane resin is less than 0.1 parts by mass based on 100 parts by mass of the resin solid content in the resin composition.

[0189] <<Benzoxazine compounds>>

[0190] The resin composition of the present embodiment may contain a benzoxazine compound.

[0191] The benzoxazine compound is not particularly limited as long as it is a compound having two or more (preferably 2 to 12, more preferably 2 to 6, further preferably 2 to 4, further preferably 2 or 3, and further preferably 2) dihydrobenzoxazine rings in one molecule, and a wide range of compounds commonly used in the field of printed wiring boards can be used.

[0192] Examples of the benzoxazine compound include bisphenol A type benzoxazine BA-BXZ (manufactured by Konishi Chemical Co., Ltd.), bisphenol F type benzoxazine BF-BXZ (manufactured by Konishi Chemical Co., Ltd.), and bisphenol S type benzoxazine BS-BXZ (manufactured by Konishi Chemical Co., Ltd.).

[0193] The resin composition of the present embodiment preferably contains a benzoxazine compound within a range that does not impair the effects of the present invention. When the resin composition of the present embodiment contains a benzoxazine compound, the content thereof is preferably 0.1 parts by mass or more and preferably 50 parts by mass or less relative to 100 parts by mass of the resin solid content in the resin composition.

[0194] The resin composition in the present embodiment may contain only one benzoxazine compound or two or more benzoxazine compounds. When containing two or more benzoxazine compounds, the total amount is preferably within the above range.

[0195] The resin composition in the present embodiment may also be configured to contain substantially no benzoxazine compound. Substantially containing no benzoxazine compound means that the content of the benzoxazine compound is less than 0.1 parts by mass based on 100 parts by mass of the resin solid content in the resin composition.

[0196] <<Compounds having a polymerizable unsaturated group other than the compound (B) having two or more carbon-carbon unsaturated double bonds>>

[0197] The resin composition of the present embodiment may contain a compound having a polymerizable unsaturated group other than the compound (B) containing two or more carbon-carbon unsaturated double bonds. The number of unsaturated groups in the aforementioned compound is 1 or more per molecule, preferably 2 to 12, more preferably 2 to 6, further preferably 2 to 4, still more preferably 2 or 3, and further still more preferably 2.

[0198] The compound having a polymerizable unsaturated group other than the compound (B) having two or more carbon-carbon unsaturated double bonds is not particularly limited, and a wide range of compounds commonly used in the field of printed wiring boards can be used.

[0199] Specific examples of the compound having a polymerizable unsaturated group other than the compound (B) containing two or more carbon-carbon unsaturated double bonds include vinyl compounds (e.g., ethylene, propylene, styrene, divinylbenzene, divinylbiphenyl, etc.), acrylates (e.g., methyl (meth)acrylate, etc.), (meth)acrylates of mono- or polyols (e.g., 2-hydroxypropyl (meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc.), epoxy (meth)acrylates (e.g., bisphenol A type epoxy (meth)acrylate, bisphenol F type epoxy (meth)acrylate, etc.), and benzocyclobutene resins.

[0200] The resin composition of the present embodiment preferably includes a compound with an unsaturated group that can be polymerized except the compound (B) containing more than two carbon-carbon unsaturated double bonds within the range that does not damage the effect of the present invention. In the case where the resin composition of the present embodiment contains a compound with an unsaturated group that can be polymerized except the compound (B) containing more than two carbon-carbon unsaturated double bonds, its content is relative to 100 parts by mass of the resin solid content in the resin composition, preferably more than 0.1 parts by mass, preferably less than 50 parts by mass.

[0201] The resin composition in the present embodiment may contain only one compound having a polymerizable unsaturated group other than the compound (B) containing two or more carbon-carbon unsaturated double bonds, or may contain two or more compounds having a polymerizable unsaturated group other than the compound (B) containing two or more carbon-carbon unsaturated double bonds. When containing two or more, the total amount is preferably within the above range.

[0202] In addition, the resin composition in the present embodiment can also be set to be substantially free of: the composition of the compound with polymerizable unsaturated groups other than the compound (B) containing more than 2 carbon-carbon unsaturated double bonds. Substantially free means that the content of the compound with polymerizable unsaturated groups other than the compound (B) containing more than 2 carbon-carbon unsaturated double bonds is less than 0.1 mass parts relative to 100 mass parts of the resin solids in the resin composition.

[0203] <<Cyanate ester compounds>>

[0204] The resin composition of the present embodiment may contain a cyanate compound.

[0205] The cyanate compound is not particularly limited as long as it is a compound containing one or more (preferably 2 to 12, more preferably 2 to 6, further preferably 2 to 4, further preferably 2 or 3, and further preferably 2) cyanate groups (cyano groups) in one molecule, and compounds commonly used in the field of printed circuit boards can be widely used. In addition, the cyanate compound is preferably a compound in which the cyanate group is directly bonded to an aromatic skeleton (aromatic ring).

[0206] As the cyanate compound, for example, at least one selected from the group consisting of phenol novolac type cyanate compound, naphthol aralkyl type cyanate compound (naphthol aralkyl type cyanate), naphthol ether type cyanate compound, biphenyl aralkyl type cyanate compound, xylene resin type cyanate compound, trisphenol methane type cyanate compound, adamantane skeleton type cyanate compound, bisphenol M type cyanate compound, bisphenol A type cyanate compound, and diallyl bisphenol A type cyanate compound can be cited. Among these, from the viewpoint of further improving the low water absorption of the obtained cured product, at least one selected from the group consisting of phenol novolac type cyanate compound, naphthol aralkyl type cyanate compound, naphthol ether type cyanate compound, xylene resin type cyanate compound, bisphenol M type cyanate compound, bisphenol A type cyanate compound, and diallyl bisphenol A type cyanate compound is preferred, and naphthol aralkyl type cyanate compound is more preferred. These cyanate compounds can be prepared by a known method, and commercial products can also be used. It should be noted that the cyanate compounds having a naphthol aralkyl skeleton, a naphthyl ether skeleton, a xylene skeleton, a triphenol methane skeleton, or an adamantane skeleton have a large functional group equivalent number and a small number of unreacted cyanate groups, so that the cured products of the resin compositions using these tend to have low water absorption and further excellent. In addition, there is a tendency that the coating adhesion is further improved mainly due to the presence of an aromatic skeleton or an adamantane skeleton.

[0207] The resin composition of the present embodiment preferably includes a cyanate compound within the range of not damaging the effect of the present invention. In the case where the resin composition of the present embodiment includes a cyanate compound, the lower limit of its content is relative to 100 mass parts of resin solids in the resin composition, preferably more than 1 mass part, more preferably more than 10 mass parts, and further preferably more than 20 mass parts. The content of the cyanate compound is more than 1 mass part, preferably more than 10 mass parts, and more preferably more than 20 mass parts, so that the heat resistance, combustion resistance, chemical resistance, low dielectric constant, low dielectric loss tangent, and insulation of the obtained cured product are improved. For the upper limit of the content of the cyanate compound, in the case where the resin composition of the present embodiment includes a cyanate compound, relative to 100 mass parts of resin solids in the resin composition, preferably less than 90 mass parts, more preferably less than 80 mass parts, further preferably less than 70 mass parts, also preferably less than 60 mass parts, and further preferably less than 50 mass parts.

[0208] The resin composition in the present embodiment may contain only one cyanate compound or two or more cyanate compounds. When containing two or more cyanate compounds, the total amount is preferably within the above range.

[0209] In addition, the resin composition in the present embodiment may also be configured to be substantially free of cyanate compounds. Substantially free means that the content of cyanate compounds is less than 0.1 parts by mass, preferably less than 0.01 parts by mass, and further less than 0.001 parts by mass relative to 100 parts by mass of the resin solids in the resin composition.

[0210] <<Elastomer>>

[0211] The resin composition of the present embodiment may contain an elastomer.

[0212] In the present embodiment, the elastomer is not particularly limited, and for example, at least one selected from the group consisting of polyisoprene, polybutadiene, styrene butadiene, butyl rubber, ethylene propylene rubber, styrene butadiene ethylene, styrene butadiene styrene, styrene isoprene styrene, styrene ethylene butylene styrene, styrene propylene styrene, styrene ethylene propylene styrene, fluororubber, silicone rubber, hydrogenated compounds thereof, alkyl compounds thereof, and copolymers thereof can be cited. Among these, from the viewpoint of excellent electrical properties, at least one selected from the group consisting of styrene butadiene, styrene butadiene ethylene, styrene butadiene styrene, styrene isoprene styrene, styrene ethylene butylene styrene, styrene propylene styrene, styrene ethylene propylene styrene, hydrogenated compounds thereof, alkyl compounds thereof, and copolymers thereof is preferred, and from the viewpoint of excellent compatibility with the compound (B) containing two or more carbon-carbon unsaturated double bonds, at least one selected from the group consisting of styrene butadiene rubber, butadiene rubber, and isoprene rubber is more preferred.

[0213] In this embodiment, from the viewpoint of excellent electrical properties, the SP value of the elastomer is preferably 9 (cal / cm 3 ) 1 / 2 Hereinafter, the SP value is called the dissolution parameter, which is calculated by 3 The square root of the heat of evaporation required for the liquid to evaporate (cal / cm 3 ) 1 / 2 Generally, the smaller the value, the lower the polarity, and the closer the value, the higher the affinity between the two components. If the SP value of the elastomer is 9 (cal / cm 3 ) 1 / 2 Next, the electrical properties of the resin composition suitable for use in a printed wiring board for high-frequency applications can be obtained.

[0214] In the present embodiment, if the weight average molecular weight of the elastomer based on the polystyrene conversion by the GPC method is 80,000 or more and it is solid at 25°C, it is preferred because crack resistance is further improved when used in printed circuit board materials (e.g., laminates, metal foil-clad laminates), etc. On the other hand, if the weight average molecular weight based on the polystyrene conversion by the GPC method is 40,000 or less and it is liquid at 25°C, the warpage of the elastomer applied to a film when attached to a substrate is reduced, and therefore it becomes particularly suitable as a laminate material for a printed circuit board.

[0215] The resin composition of the present embodiment preferably contains an elastomer within a range that does not impair the effects of the present invention. When the resin composition of the present embodiment contains an elastomer, its content is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and further preferably 2 parts by mass or more relative to 100 parts by mass of the resin solid component in the resin composition. Regarding the upper limit of the content of the elastomer, when the resin composition of the present embodiment contains an elastomer, relative to 100 parts by mass of the resin solid component in the resin composition, it is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, further preferably 20 parts by mass or less, further preferably 10 parts by mass or less, and further preferably 8 parts by mass or less.

[0216] The resin composition in the present embodiment may contain only one type of elastomer or two or more types of elastomers. When containing two or more types of elastomers, the total amount is preferably within the above range.

[0217] The resin composition in the present embodiment may be configured to contain substantially no elastomer. Substantially containing no elastomer means that the content of the elastomer is less than 0.1 parts by mass based on 100 parts by mass of the resin solid content in the resin composition.

[0218] <<Silane coupling agent>>

[0219] The resin composition of the present embodiment may further contain a silane coupling agent. By containing a silane coupling agent, there is a tendency that the dispersibility of the filler (D) described below and the bonding strength between the resin component, the filler (D), and the substrate described below are further improved.

[0220] The silane coupling agent is not particularly limited as long as it is a silane coupling agent generally used for surface treatment of inorganic substances, and examples thereof include vinyl silane compounds such as vinyl trimethoxysilane; styryl silane compounds such as p-styryl trimethoxysilane; amino silane compounds such as γ-aminopropyl triethoxysilane and N-β-(aminoethyl)-γ-aminopropyl trimethoxysilane; epoxy silane compounds such as γ-glycidoxypropyl trimethoxysilane; acrylic silane compounds such as γ-acryloxypropyl trimethoxysilane; cationic silane compounds such as N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyl trimethoxysilane hydrochloride; phenyl silane compounds, etc. The silane coupling agent may be used alone or in combination of two or more.

[0221] When the resin composition of the present embodiment contains a silane coupling agent, the lower limit of the content thereof is preferably 0.005 parts by mass or more, more preferably 0.01 parts by mass or more, and further preferably 0.1 parts by mass or more, relative to 100 parts by mass of the resin solid component in the resin composition. In addition, the upper limit of the content of the silane coupling agent is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and further preferably 2 parts by mass or less, relative to 100 parts by mass of the resin solid component in the resin composition.

[0222] The silane coupling agent may be used alone or in combination of two or more. When two or more are used, the total amount is within the above range.

[0223] <<Active ester compounds>>

[0224] The resin composition of the present embodiment may contain an active ester compound.

[0225] The active ester compound is not particularly limited, and examples thereof include compounds having two or more (preferably 2 to 12, more preferably 2 to 6, further preferably 2 to 4, further preferably 2 or 3, and further preferably 2) active ester groups in one molecule.

[0226] The active ester compound can be a straight chain, branched chain or cyclic compound. Among these, from the aspect of improving the heat resistance of the obtained cured product, the active ester compound obtained by reacting a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound is preferred, the active ester compound obtained by reacting a carboxylic acid compound with one or more compounds selected from the group consisting of a phenol compound, a naphthol compound and a thiol compound is more preferred, the aromatic compound obtained by reacting a carboxylic acid compound with an aromatic compound having a phenolic hydroxyl group and having two or more active ester groups in one molecule is further preferred, and the aromatic compound obtained by reacting a compound having at least two or more carboxylic acids in one molecule with an aromatic compound having a phenolic hydroxyl group and having two or more active ester groups in one molecule is particularly preferred.

[0227] Examples of the carboxylic acid compound include at least one selected from the group consisting of benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid and pyromellitic acid. Among these, from the viewpoint of further improving the heat resistance of the obtained cured product, at least one selected from the group consisting of succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid and terephthalic acid is preferred, and at least one selected from the group consisting of isophthalic acid and terephthalic acid is more preferred.

[0228] Examples of the thiocarboxylic acid compound include one or more selected from thioacetic acid and thiobenzoic acid.

[0229] Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol , dicyclopentadienyl diphenol and phenol novolac, and from the viewpoint of further improving the heat resistance and solvent solubility of the obtained cured product, preferably bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, ... tetrahydroxybenzophenone, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, tetrahydroxybenzophenone, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, tetrahydroxybenzophenone, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, di At least one selected from the group consisting of naphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyl diphenol and phenol novolac, particularly preferably at least one selected from the group consisting of dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyl diphenol and phenol novolac (preferably at least one selected from the group consisting of dicyclopentadienyl diphenol and phenol novolac, more preferably dicyclopentadienyl diphenol).

[0230] Examples of the thiol compound include one or more selected from the group consisting of benzenedithiol and triazine dimethiol.

[0231] In addition, for the active ester compound, from the viewpoint of improving the compatibility with the epoxy compound, a compound having at least two or more carboxylic acids in one molecule and containing an aliphatic chain is preferred, and from the viewpoint of improving the heat resistance, a compound having an aromatic ring is preferred. As more specific active ester compounds, active ester compounds described in Japanese Patent Application Laid-Open No. 2004-277460 can be cited.

[0232] Active ester compound can use commercially available products, can be prepared by known methods.As commercially available products, can enumerate the compound (for example EXB9451, EXB9460, EXB9460S, HPC-8000-65T (all DIC Co., Ltd. system) etc. comprising dicyclopentadienyl diphenol structure), acetylated product (for example DC808 (Mitsubishi Chemical Corporation system)) of phenol novolac and benzoylated product (for example YLH1026, YLH1030, YLH1048 (all Mitsubishi Chemical Corporation system)) of phenol novolac, from the viewpoint that the low thermal expansion coefficient of (cured product) is improved when the storage stability of varnish and the resin composition are cured, preferably EXB9460S.

[0233] The active ester compound can be prepared by a known method, for example, by a condensation reaction of a carboxylic acid compound and a hydroxy compound. As a specific example, the following method can be cited: (a) a carboxylic acid compound or its halide, (b) a hydroxy compound, and (c) an aromatic monohydroxy compound are reacted in a ratio of 0.05 to 0.75 moles of phenolic hydroxyl groups (b) to 0.25 to 0.95 moles of (c) relative to 1 mole of carboxyl groups or acyl halide groups of (a), 0.05 to 0.75 moles of phenolic hydroxyl groups (b), and 0.25 to 0.95 moles of (c).

[0234] The active ester compound is preferably contained within a range that does not impair the effects of the present invention. When the resin composition of the present embodiment contains an active ester compound, the amount is preferably 1 part by mass or more and preferably 90 parts by mass or less per 100 parts by mass of the resin solid content in the resin composition.

[0235] The resin composition in the present embodiment may contain only one active ester compound, or may contain two or more active ester compounds. When containing two or more active ester compounds, the total amount is preferably within the above range.

[0236] The resin composition in the present embodiment may be configured to contain substantially no active ester compound. Substantially containing no active ester compound means that the content of the active ester compound is less than 1 part by mass based on 100 parts by mass of the resin solid content in the resin composition.

[0237] <(D) Filling material>

[0238] The resin composition of the present embodiment preferably contains a filler (D). By adding the filler (D), the low dielectric constant, low dielectric loss tangent, flame retardancy, and low thermal expansion of the resin composition can be further improved.

[0239] In addition, the filler (D) used in the present embodiment preferably has excellent dielectric properties. For example, the dielectric constant (Dk) of the filler (D) used in the present embodiment measured by the resonant cavity perturbation method is preferably 8.0 or less, more preferably 6.0 or less. In addition, the lower limit of the aforementioned dielectric constant is, for example, actually greater than 2.0. In addition, the dielectric loss tangent (Df) of the filler (D) used in the present embodiment measured by the resonant cavity perturbation method is preferably 0.05 or less, more preferably less than 0.01. In addition, the lower limit of the aforementioned dielectric loss tangent is, for example, actually greater than 0.0001.

[0240] The filler (D) used in this embodiment is not particularly limited in type, and can be used by common users in the field. Specifically, in addition to natural silica, fused silica, synthetic silica, amorphous silica, Aerosil, hollow silica and other silicas, white carbon, titanium dioxide, zinc oxide, magnesium oxide, zirconium oxide, boron nitride, aggregated boron nitride, silicon nitride, aluminum nitride, barium sulfate, aluminum hydroxide, aluminum hydroxide heat-treated product (aluminum hydroxide is heated to reduce a portion of the crystal water), boehmite, magnesium hydroxide and other metal hydrates, molybdenum oxide, zinc molybdate and other molybdenum compounds, zinc borate, zinc stannate, aluminum oxide, clay, kaolin, slip In addition to inorganic fillers such as stone, calcined clay, calcined kaolin, calcined talc, mica, E-glass, A-glass, NE-glass, C-glass, L-glass, D-glass, S-glass, M-glass G20, glass staple fibers (including glass micropowders such as E-glass, T-glass, D-glass, S-glass, and Q-glass), hollow glass, and spherical glass, organic fillers such as styrene-type, butadiene-type, acrylic-type rubber powders, core-shell-type rubber powders, silicone resin powders, silicone rubber powders, and silicone composite powders can also be cited.

[0241] Among these, one or more selected from the group consisting of silica, aluminum hydroxide, boehmite, magnesium oxide and magnesium hydroxide are suitable. By using these fillers, the thermal expansion characteristics, dimensional stability, flame retardancy and other characteristics of the resin composition are improved.

[0242] The content of the filler (D) in the resin composition of the present embodiment can be appropriately set according to the desired characteristics, and is not particularly limited. It is preferably 50 parts by mass or more, and more preferably 75 parts by mass or more, relative to 100 parts by mass of the resin solid component in the resin composition. In addition, relative to 100 parts by mass of the resin solid component in the resin composition, it is preferably 1600 parts by mass or less, more preferably 1200 parts by mass or less, further preferably 1000 parts by mass or less, also preferably 750 parts by mass or less, and further preferably 500 parts by mass or less, further preferably 300 parts by mass or less, and can also be 250 parts by mass or less, or 200 parts by mass or less.

[0243] In the resin composition of the present embodiment, as an example of a preferred embodiment, the content of the filler (D) can be 30% by mass to 80% by mass of the components excluding the solvent.

[0244] The resin composition in the present embodiment may contain only one filler (D) or two or more fillers (D). When containing two or more fillers, the total amount is preferably within the above range.

[0245] <Flame retardant>

[0246] The resin composition of the present embodiment may contain a flame retardant.

[0247] As the flame retardant, known substances can be used, for example, brominated epoxy resin, brominated polycarbonate, brominated polystyrene, brominated styrene, brominated phthalimide, tetrabromobisphenol A, pentabromobenzyl (meth) acrylate, pentabromotoluene, tribromophenol, hexabromobenzene, decabromodiphenyl ether, bis-1,2-pentabromophenylethane, chlorinated polystyrene, chlorinated paraffin and other halogen flame retardants, red phosphorus, tricresyl phosphate, triphenyl phosphate, cresyl diphenyl phosphate, tri(phenyl) phosphate, etc. Phosphorus flame retardants such as 1,3-phenylenebis(2,6-di(xylyl)phosphate), 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, aluminum hydroxide, magnesium hydroxide, some boehmite, boehmite, zinc borate, antimony trioxide, and silicone flame retardants such as silicone rubber and silicone resin. These flame retardants can be used alone or in combination of two or more. Among these, 1,3-phenylenebis(2,6-di(xylyl)phosphate) is preferred because it does not damage the low dielectric property.

[0248] When the resin composition of the present embodiment contains a flame retardant, the content thereof is preferably 0.1% by mass or more of the resin composition, and is preferably 20% by mass or less, and more preferably 10% by mass or less.

[0249] The flame retardant may be used alone or in combination of two or more. When two or more flame retardants are used, the total amount is within the above range.

[0250] <Dispersant>

[0251] The resin composition of the present embodiment may include a dispersant. As a dispersant, it is suitable for users of common coatings, and its type is not particularly limited. The dispersant preferably uses a copolymer-based wetting dispersant, and as a specific example thereof, DISPERBYK (registered trademark) -110, 111, 161, 180, 2009, 2152, 2155, BYK (registered trademark) -W996, W9010, W903, W940, etc. made by BYK Japan Co., Ltd. can be cited.

[0252] When the resin composition of the present embodiment includes a dispersant, the lower limit of its content is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and can be 0.3 parts by mass or more relative to 100 parts by mass of the resin solid component in the resin composition. In addition, the upper limit of the content of the above-mentioned dispersant is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and further preferably 3 parts by mass or less relative to 100 parts by mass of the resin solid component in the resin composition.

[0253] The dispersants may be used alone or in combination of two or more. When two or more are used, the total amount is within the above range.

[0254] <Curing accelerator>

[0255] The resin composition of this embodiment may further include a curing accelerator. The curing accelerator is not particularly limited, and examples thereof include imidazoles such as triphenylimidazole; organic peroxides such as benzoyl peroxide, lauroyl peroxide, acetyl peroxide, p-chlorobenzoyl peroxide, di-tert-butyl diperphthalate; azo compounds such as azodicarbonitrile; N,N-dimethylbenzylamine, N,N-dimethylaniline, N,N-dimethyltoluidine, 2-N-ethylanilinoethanol, tri-n-butylamine, pyridine, quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, tetramethylbutanediamine , N-methylpiperidine and other tertiary amines; phenols such as phenol, xylenol, cresol, resorcinol, catechol and other phenols; organic metal salts such as lead naphthenate, lead stearate, zinc naphthenate, zinc octoate, manganese octoate, tin oleate, dibutyltin maleate, manganese naphthenate, cobalt naphthenate, ferric acetylacetonate, etc.; those prepared by dissolving these organic metal salts in hydroxyl-containing compounds such as phenol and bisphenol; inorganic metal salts such as tin chloride, zinc chloride, aluminum chloride, etc.; dioctyltin oxide, and other organic tin compounds such as alkyl tin and alkyl tin oxide, etc.

[0256] Preferred curing accelerators are imidazoles and organic metal salts, and more preferably, they are used in combination.

[0257] When the resin composition of the present embodiment includes a curing accelerator, the lower limit of its content is preferably 0.005 mass parts or more, more preferably 0.01 mass parts or more, and further preferably 0.1 mass parts or more relative to 100 mass parts of the resin solids in the resin composition. In addition, the upper limit of the content of the aforementioned curing accelerator is preferably 10 mass parts or less, more preferably 5 mass parts or less, and further preferably 2 mass parts or less relative to 100 mass parts of the resin solids in the resin composition.

[0258] The curing accelerator may be used alone or in combination of two or more. When two or more are used, the total amount is within the above range.

[0259] <Solvent>

[0260] The resin combination of the present embodiment can contain a solvent, preferably an organic solvent.Containing a solvent, the resin combination of the present embodiment is at least a portion of the above-mentioned various resin solid components, preferably all dissolved or soluble in the form (solution or varnish) of the solvent.As a solvent, as long as it is a polar organic solvent or a non-polar organic solvent that can make at least a portion of the above-mentioned various resin solid components, preferably all dissolved or soluble, there is no particular limitation, as a polar organic solvent, for example, ketones (such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), cellosolves (such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.), esters (such as ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate, methyl hydroxyisobutyrate, etc.), amides (such as dimethoxyacetamide, dimethylformamide, etc.), as a non-polar organic solvent, aromatic hydrocarbons (such as toluene, xylene, etc.) can be cited.

[0261] The solvent may be used alone or in combination of two or more. When two or more solvents are used, the total amount is within the above range.

[0262] <Other ingredients>

[0263] The resin composition of the present embodiment may contain thermoplastic resins, various polymer compounds such as oligomers thereof, and various additives in addition to the above-mentioned components. As additives, ultraviolet light absorbers, antioxidants, photopolymerization initiators, fluorescent whitening agents, photosensitizers, dyes, pigments, thickeners, flow regulators, lubricants, defoamers, leveling agents, glossing agents, polymerization inhibitors, etc. These additives may be used alone or in combination of two or more.

[0264] <Application>

[0265] The resin composition of the present embodiment is used as a cured product. Specifically, the resin composition of the present embodiment can be suitable as a low dielectric constant material and / or a low dielectric loss tangent material, as an insulating layer of a printed circuit board, a semiconductor packaging material, etc., and an electronic material resin composition. The resin composition of the present embodiment can be suitable as a prepreg, a metal foil laminated plate using a prepreg, a resin sheet, and a printed circuit board material.

[0266] The resin composition of the present embodiment is used as a layered material (mainly including film, sheet, etc.) of an insulating layer, prepreg, resin sheet, etc. of a printed circuit board. When the above-mentioned layered material is formed, its thickness is preferably 5 μm or more, more preferably 10 μm or more. As the upper limit of the thickness, it is preferably 200 μm or less, more preferably 180 μm or less. It should be noted that, for example, when the resin composition of the present embodiment is impregnated with glass cloth, the thickness of the above-mentioned layered material refers to the thickness including the glass cloth.

[0267] The material formed from the resin composition of this embodiment can be used for applications where patterning is performed by exposure and development, or can be used for applications where exposure and development are not performed. The material is particularly suitable for applications where exposure and development are not performed.

[0268] <<Prepreg>>

[0269] The prepreg of the present embodiment is formed by a substrate (prepreg substrate) and a resin composition of the present embodiment. The prepreg of the present embodiment can be obtained, for example, as follows: after applying (e.g., impregnating and / or coating) the resin composition of the present embodiment to a substrate, semi-curing is performed by heating (e.g., a method of drying at 120 to 220° C. for 2 to 15 minutes, etc.), thereby obtaining. In this case, the amount of the resin composition attached to the substrate, that is, the amount of the resin composition (including the filler (D)) relative to the total amount of the semi-cured prepreg is preferably in the range of 20 to 99% by mass, and more preferably in the range of 20 to 80% by mass.

[0270] The substrate is not particularly limited as long as it is a substrate used for various printed circuit board materials. Examples of the material of the substrate include glass fibers (e.g., E-glass, D-glass, L-glass, S-glass, T-glass, Q-glass, UN-glass, NE-glass, spherical glass, etc.), inorganic fibers other than glass (e.g., quartz, etc.), and organic fibers (e.g., polyimide, polyamide, polyester, liquid crystal polyester, polytetrafluoroethylene, etc.). The form of the substrate is not particularly limited, and examples include woven fabrics, non-woven fabrics, rovings, chopped fiber mats, cushioning mats, etc. These substrates may be used alone or in combination of two or more. Among these substrates, from the viewpoint of dimensional stability, woven fabrics that have been subjected to super fiber opening treatment and filling treatment are preferred. From the viewpoint of strength and low water absorption, the substrate preferably has a thickness of less than 200 μm and a mass of 250 g / m 2 The following glass woven fabrics are preferably those which have been surface treated with a silane coupling agent such as epoxy silane treatment or amino silane treatment from the viewpoint of moisture absorption and heat resistance. From the viewpoint of electrical properties, low dielectric glass cloths formed of glass fibers having low dielectric constant and low dielectric loss tangent such as L-glass, NE-glass, and Q-glass are more preferred.

[0271] Examples of substrates with low dielectric constants include substrates with dielectric constants of 5.0 or less (preferably 3.0 to 4.9). Examples of substrates with low dielectric loss tangents include substrates with dielectric loss tangents of 0.006 or less (preferably 0.001 to 0.005). The dielectric constant and dielectric loss tangent are values ​​measured at 10 GHz using a perturbation cavity resonator.

[0272] <<Metal foil-clad laminate>>

[0273] The metal foil clad laminate of the present embodiment comprises: a layer formed by at least one prepreg of the present embodiment, and a metal foil disposed on one or both sides of the layer formed by the aforementioned prepreg. As a method for making the metal foil clad laminate of the present embodiment, for example, the following method can be cited: at least one (preferably overlapping two or more) prepreg of the present embodiment is disposed, and a metal foil is disposed on one or both sides thereof and laminated. In more detail, a metal foil of copper, aluminum, etc. is disposed on one or both sides of the prepreg and laminated, so that it can be made. As the number of prepregs, preferably 1 to 10, more preferably 2 to 10, and further preferably 2 to 9. As a metal foil, as long as it is a metal foil used for a printed circuit board material, there is no particular limitation, for example, copper foils such as rolled copper foil and electrolytic copper foil can be cited. The thickness of the metal foil (preferably copper foil) is not particularly limited and can be about 1.5 to 70 μm. As the molding method, there can be mentioned the method generally used when molding into a laminated board and a multilayer board for a printed circuit board. More specifically, there can be mentioned the following method: using a multistage press, a multistage vacuum press, a continuous molding machine, an autoclave molding machine, etc., at a temperature of about 180 to 350° C., a heating time of about 100 to 300 minutes, a surface pressure of 20 to 100 kg / cm 2 The prepreg of the present embodiment is combined with a circuit board for the inner layer prepared separately and laminated to form a multilayer board. As a method for manufacturing a multilayer board, for example, a copper foil of about 35 μm is arranged on both sides of one prepreg of the present embodiment, and after lamination by the above-mentioned molding method, an inner layer circuit is formed, and a blackening treatment is applied to the circuit to form an inner layer circuit board. After that, the inner layer circuit board and the prepreg of the present embodiment are alternately arranged one by one, and copper foil is further arranged in the outermost layer. Under the above-mentioned conditions, preferably under vacuum, lamination molding is performed to produce a multilayer board. The metal foil-clad laminate of the present embodiment can be suitable for use as a printed circuit board.

[0274] The metal foil-clad laminate of the present embodiment preferably has a low dielectric constant (Dk) measured using a laminate A from which the metal foil has been removed by etching. Specifically, the dielectric constant (Dk) of the laminate A is preferably 3.5 or less, more preferably 3.4 or less, and further preferably 3.3 or less. There is no particular limitation on the lower limit of the dielectric constant (Dk), and for example, it is actually 2.0 or more.

[0275] In addition, the metal foil-clad laminate of the present embodiment preferably has a low dielectric loss tangent (Df) measured using a laminate A from which the metal foil has been removed by etching. Specifically, the dielectric loss tangent (Df) is preferably 0.0040 or less, more preferably 0.0035 or less, and further preferably 0.0030 or less. There is no particular limitation on the lower limit of the dielectric loss tangent (Df), and for example, it is actually 0.0001 or more.

[0276] The dielectric constant (Dk) and the dielectric loss tangent (Df) were measured according to the method described in the examples described later.

[0277] In addition, the metal foil-clad laminate of the present embodiment preferably has a high glass transition temperature measured using a laminate A from which the metal foil has been removed by etching. Specifically, the glass transition temperature of the laminate A is preferably 180° C. or higher, more preferably 280° C. or higher. The upper limit of the glass transition temperature is, for example, 400° C. or lower in practice. The glass transition temperature of the metal foil-clad laminate is measured according to the description of the examples described later.

[0278] The metal foil-clad laminate of the present embodiment preferably has a water absorption of 0.8% by mass or less, more preferably 0.4% by mass or less, further preferably 0.35% by mass or less, and still more preferably 0.20% by mass or less, after being treated at 121° C. and 2 atmospheres for 1 hour using a pressure cooker tester in accordance with JIS C6485:2008. The lower limit of the water absorption is, for example, 0% by mass.

[0279] In addition, the metal foil-clad laminate of the present embodiment preferably has a water absorption of 0.8% by mass or less, more preferably 0.4% by mass or less, further preferably 0.35% by mass or less, and still more preferably 0.20% by mass or less, after being treated at 121° C. and 2 atmospheres for 5 hours using a pressure cooker tester in accordance with JIS C6485:2008. The lower limit of the water absorption is, for example, 0% by mass.

[0280] As described above, the resin composition for electronic materials obtained using the resin composition of the present embodiment (a resin composition formed by a combination of specific components) has the characteristics that its cured product has excellent heat resistance, low dielectric properties (low dielectric constant, low dielectric loss tangent) and low water absorption, and further has excellent chemical resistance and desmear resistance.

[0281] <<Printed Circuit Board>>

[0282] The printed circuit board of the present embodiment comprises: an insulating layer, and a conductor layer disposed on the surface of the aforementioned insulating layer, and the aforementioned insulating layer comprises: at least one of a layer formed by the resin composition of the present embodiment and a layer formed by the prepreg of the present embodiment. This printed circuit board can be manufactured according to conventional methods, and its manufacturing method is not particularly limited. Below, an example of a method for manufacturing a printed circuit board is shown. First, a metal foil-clad laminate such as the above-mentioned metal foil-clad laminate is prepared. Next, the surface of the metal foil-clad laminate is subjected to etching treatment to form an inner layer circuit, and an inner layer substrate is prepared. The inner layer circuit surface of the inner layer substrate is subjected to surface treatment for improving the bonding strength as required, and then the required number of prepregs are overlapped on the inner layer circuit surface, and the metal foil for the outer layer circuit is further laminated on its outer side, and heated and pressed to form an integral body. In this way, a multilayer laminate having an insulating layer formed by a cured product of a substrate and a resin composition is formed between the metal foil for the inner layer circuit and the outer layer circuit. Then, after the multi-layer laminate is subjected to hole opening processing for through holes and conductive holes, a metal-plated coating is formed on the wall surface of the hole to connect the metal foil used for the inner layer circuit and the outer layer circuit. The metal foil used for the outer layer circuit is further etched to form the outer layer circuit, thereby manufacturing a printed circuit board.

[0283] The printed circuit board obtained in the above manufacturing example has an insulating layer and a conductor layer formed on the surface of the insulating layer, and the insulating layer becomes a structure containing the resin composition of the above embodiment and / or its cured product. That is, the layer formed by the prepreg of the above embodiment (for example, a prepreg formed by a substrate and the resin composition of the present embodiment impregnated or coated thereon) and the layer formed by the resin composition of the metal foil-clad laminate of the above embodiment become the insulating layer of the present embodiment.

[0284] <<Resin Sheet>>

[0285] The resin sheet of the present embodiment comprises: a support, and a layer formed by the resin composition of the present embodiment disposed on the surface of the aforementioned support. The resin sheet can be used as a laminated film or a dry film solder resist. There is no particular limitation on the method for manufacturing the resin sheet, and for example, the following method can be cited: a solution in which the resin composition of the present embodiment is dissolved in a solvent is applied (coated) to the support and dried to obtain a resin sheet.

[0286] Examples of the support used herein include polyethylene films, polypropylene films, polycarbonate films, polyethylene terephthalate films, ethylene tetrafluoroethylene copolymer films, release films having release agents coated on the surfaces of these films, organic film substrates such as polyimide films, conductor foils such as copper foil and aluminum foil, glass plates, SUS (Steel Use Stainless) plates, and FRP (Fiber-Reinforced Plastics) plates, but are not particularly limited.

[0287] As a coating method (applying method), for example, the following method can be cited: a solution in which the resin composition of the present embodiment is dissolved in a solvent is coated on a support using a rod coater, a die coater, a scraper, a Baker dispenser, etc. In addition, after drying, the support is peeled off or etched from a resin sheet on which the support and the resin composition are stacked, thereby forming a single-layer sheet. It should be noted that the solution in which the resin composition of the present embodiment is dissolved in a solvent is supplied to a mold having a sheet-shaped cavity and dried, etc., to form a sheet, so that a single-layer sheet can be obtained without using a support.

[0288] It should be noted that in the preparation of the single-layer sheet or resin sheet of the present embodiment, the drying conditions when removing the solvent are not particularly limited. If it is a low temperature, the solvent is likely to remain in the resin composition. If it is a high temperature, the resin composition is cured. Therefore, it is preferably at a temperature of 20°C to 200°C for 1 to 90 minutes. In addition, the single-layer sheet or resin sheet can be used in an uncured state after only the solvent is dried, or it can be used in a semi-cured (B-stage) state as needed. Furthermore, the thickness of the resin layer in the single-layer sheet or resin sheet of the present embodiment can be adjusted according to the concentration of the solution of the resin composition of the present embodiment used for coating (applying) and the coating thickness. There are no special restrictions. Generally, if the coating thickness becomes thicker, the solvent becomes easy to remain during drying. Therefore, it is preferably 0.1 to 500 μm.

[0289] Example

[0290] Below, enumerate embodiment, the present invention is further specifically described.Material, dosage, ratio, processing content, processing step etc. shown in the following embodiment can be suitably changed as long as do not depart from the gist of the present invention.Therefore, the scope of the present invention is not limited to the specific example shown below.

[0291] When the measuring equipment used in the examples is difficult to obtain due to discontinuation of production or the like, other equipment having equivalent performance may be used for measurement.

[0292] <Synthesis Example 1 Synthesis of modified polyphenylene ether compound>

[0293] <<Synthesis of bifunctional phenylene ether oligomer>>

[0294] In a 12L vertical reactor equipped with a stirrer, a thermometer, an air inlet pipe and a baffle, 9.36g (42.1mmol) of CuBr2, 1.81g (10.5mmol) of N,N'-di-tert-butylethylenediamine, 67.77g (671.0mmol) of n-butyldimethylamine and 2600g of toluene were added, and stirred at a reaction temperature of 40°C while a mixed gas of nitrogen and air adjusted to an oxygen concentration of 8% by volume was introduced at a flow rate of 5.2L / min to the pre- A mixed solution of 129.32 g (0.48 mol) of 2,2',3,3',5,5'-hexamethyl-(1,1'-biphenol)-4,4'-diol, 878.4 g (7.2 mol) of 2,6-dimethylphenol, 1.22 g (7.2 mmol) of N,N'-di-tert-butylethylenediamine, and 26.35 g (260.9 mmol) of n-butyldimethylamine dissolved in 2300 g of methanol was added dropwise over 230 minutes with stirring. After the addition was completed, 1500 g of water in which 48.06 g (126.4 mmol) of tetrasodium ethylenediaminetetraacetate was dissolved was added to stop the reaction. The aqueous layer and the organic layer were separated, and the organic layer was washed with a 1N hydrochloric acid aqueous solution and then with pure water. The obtained solution was concentrated to 50% by mass in an evaporator to obtain 1981 g of a toluene solution of a bifunctional phenylene ether oligomer (resin "A"). The number average molecular weight of the resin “A” in terms of polystyrene based on the GPC method was 1975, the weight average molecular weight in terms of polystyrene based on the GPC method was 3514, and the hydroxyl equivalent was 990.

[0295] <<Synthesis of modified polyphenylene ether compounds>>

[0296] In a reactor equipped with a stirring device, a thermometer and a reflux tube, 833.4 g of a toluene solution of resin "A", 76.7 g of vinylbenzyl chloride (manufactured by Seimi Chemical Co., Ltd., "CMS-P"), 1600 g of dichloromethane, 6.2 g of benzyldimethylamine, 199.5 g of pure water, and 83.6 g of a 30.5% by mass NaOH aqueous solution were added, and stirred at a reaction temperature of 40°C. After stirring for 24 hours, the organic layer was washed with a 1N hydrochloric acid aqueous solution and then with pure water. The obtained solution was concentrated in an evaporator, added dropwise to methanol, solidified, and the solid was recovered by filtration and vacuum dried to obtain 450.1 g of a modified polyphenylene ether compound. The number average molecular weight of the modified polyphenylene ether compound based on the polystyrene conversion of the GPC method is 2250, the weight average molecular weight based on the polystyrene conversion of the GPC method is 3920, and the vinyl equivalent is 1189 g / vinyl.

[0297] Example 1

[0298] 77 parts by mass of the compound (A) represented by formula (M1) ("X9-450", manufactured by DIC Corporation, a compound represented by formula (M1)), 20 parts by mass of the modified polyphenylene ether obtained in Synthesis Example 1, 3 parts by mass of a naphthalene skeleton-modified novolac-type epoxy resin ("HP-9900", manufactured by DIC Corporation), 150 parts by mass of fused silica ("SC2050-MNU", average particle size 0.5 μm (manufactured by Admatex Corporation)), and 0.5 parts by mass of TPIZ (2,4,5-triphenylimidazole, catalyst) were dissolved and mixed in methyl ethyl ketone to obtain a varnish. It should be noted that the above-mentioned amounts of each addition represent the solid content. The varnish was further diluted with methyl ethyl ketone, impregnated and coated on NE glass woven fabric (manufactured by Tobo Co., Ltd., product number: N3313) with a thickness of 0.069 mm, and heated and dried at 150° C. for 5 minutes to obtain a prepreg having a resin composition content (including filler) of 60% by mass, a glass cloth content of 40% by mass, and a thickness of 100 μm. The obtained prepreg was used to prepare a metal foil-clad laminate, and various physical properties were measured.

[0299] 8 prepregs were stacked, 12 μm thick electrolytic copper foil was placed on the top and bottom, and the pressure was 30 kgf / cm 2 , and the laminate molding was carried out at a temperature of 220°C for 120 minutes to obtain a metal foil-clad laminate with an insulating layer thickness of 0.8 mm. The 12 μm thick electrolytic copper foil used was 3EC-M3-VLP, manufactured by Mitsui Mining & Smelting Co., Ltd. The obtained metal foil-clad laminate or the laminate A described below was used to evaluate the formability (presence or absence of voids), glass transition temperature (Tg), dielectric constant (Dk), dielectric loss tangent (Df), water absorption, chemical resistance and desmear resistance. The evaluation results are shown in Table 1.

[0300] (Measurement method and evaluation method)

[0301] (1) Formability (presence or absence of voids)

[0302] The inside appearance (insulating layer) of the metal foil-clad laminate was visually checked, and the case where voids were confirmed was judged as "presence of voids", and the case where voids were not confirmed was judged as "no voids".

[0303] (2) Glass transition temperature (Tg)

[0304] The glass transition temperature was measured using a dynamic viscoelasticity measuring device (DMA) in accordance with JIS-K7244-4:1999 (Plastics - Test methods for dynamic mechanical properties - Part 4: Tensile vibration - non-resonance method), at a starting temperature of 30°C, an end temperature of 400°C, a heating rate of 5°C / min, a measurement frequency of 1Hz, and a nitrogen atmosphere. The dynamic viscoelasticity of a laminate (hereinafter referred to as "laminated plate A") in which the copper foil of the metal foil-clad laminate was removed by etching was measured, and the maximum value of the loss tangent (tan δ) obtained at this time was taken as the glass transition temperature. The dynamic viscoelasticity measuring device used was EXSTAR6000DMS6100 manufactured by Seiko Instruments Inc.

[0305] Evaluation was performed as follows.

[0306] A: Above 280℃

[0307] B: 180℃ or higher and lower than 280℃

[0308] C: 100℃ or higher and lower than 180℃

[0309] (3) Dielectric constant (Dk) and dielectric loss tangent (Df):

[0310] The laminated plate A was used to measure the dielectric constant (Dk) and dielectric loss tangent (Df) at 10 GHz using a perturbation method cavity resonator.

[0311] Agilent 8722ES manufactured by Agilent Technologies was used as the perturbation method cavity resonator.

[0312] Evaluation was performed as follows.

[0313] <Dk>

[0314] A: 3.3 or less

[0315] B + : More than 3.3 and less than 3.4

[0316] B - : More than 3.4 and less than 3.5

[0317] C: More than 3.5

[0318] <Df>

[0319] A: 0.0030 or less

[0320] B + : More than 0.0030 and less than 0.0035

[0321] B -: More than 0.0035 and less than 0.0040

[0322] C: more than 0.0040

[0323] Furthermore, after leaving the sample to stand for 5 hours under the conditions of 121° C. and 2 atmospheres using a pressure cooker tester, Dk and Df were measured in the same manner as above.

[0324] Evaluation was performed as follows.

[0325] <Dk(after water absorption)>

[0326] A: 3.4 or less

[0327] B: More than 3.4 and less than 3.5

[0328] C: More than 3.5

[0329] <Df(after water absorption)>

[0330] A: 0.0080 or less

[0331] B: more than 0.0080 and less than 0.0100

[0332] C: more than 0.0100

[0333] (4) Water absorption:

[0334] The laminate A was cut into samples of 30 mm × 30 mm, and the water absorption after treatment at 121° C. and 2 atmospheres for 1 hour and 5 hours was measured using a pressure cooker tester in accordance with JIS C6485: 2008. In Table 1, “1 hour” corresponds to the water absorption after treatment for 1 hour, and “5 hours” corresponds to the water absorption after treatment for 5 hours.

[0335] The pressure cooker testing machine used was a PC-3 model manufactured by Hirayama Manufacturing Co., Ltd.

[0336] Evaluation was performed as follows.

[0337] S + : 0.20 mass % or less

[0338] S - : more than 0.20 mass % and less than 0.35 mass %

[0339] A: more than 0.35 mass % and 0.4 mass % or less

[0340] B: more than 0.4 mass % and 0.8 mass % or less

[0341] C: more than 0.8 mass%

[0342] (5) Chemical resistance:

[0343] Immerse the cut laminate A into a 50 mm × 50 mm sample in a 4N 60°C hydrochloric acid aqueous solution for 1 hour or 2 hours. Calculate the mass reduction rate (mass %) from the mass of the laminate A before and after immersion. The smaller the absolute value, the better the chemical resistance (acid resistance). In addition, immerse in a 1N 70°C sodium hydroxide aqueous solution for 1 hour or 2 hours. Calculate the mass reduction rate (mass %) from the mass of the laminate A before and after immersion, and express it as an absolute value. The smaller the absolute value, the better the chemical resistance (alkali resistance).

[0344] Evaluation was performed as follows.

[0345] S: 0.3 mass % or less

[0346] A: more than 0.3 mass % and 1.0 mass % or less

[0347] B: more than 1.0 mass % and 3.0 mass % or less

[0348] C: more than 3.0 mass%

[0349] (6) Resistance to desmearing:

[0350] For laminate A, the following immersion treatment is performed. First, laminate A is immersed in a swelling solution (Swelling Dip Securigant P, manufactured by Atotech Japan Co., Ltd.) at 80°C for 10 minutes. Next, the immersed laminate A is immersed in a roughening solution (Concentrate compactCP, manufactured by Atotech Japan Co., Ltd.) at 80°C for 5 minutes. Next, the immersed laminate A is immersed in a neutralizing solution (Reduction conditioner securigant P500, manufactured by Atotech Japan Co., Ltd.) at 45°C for 10 minutes. The mass reduction rate (mass %) of laminate A after the series of immersion treatments is measured once, the mass reduction rate (mass %) after the second time, and the mass reduction rate (mass %) after the third time. In Table 1, "1 time" corresponds to "mass reduction rate (mass %) after 1 immersion treatment", "2 times" corresponds to "mass reduction rate (mass %) after 2 immersion treatments", and "3 times" corresponds to "mass reduction rate (mass %) after 3 immersion treatments". The numerical values ​​are expressed as absolute values.

[0351] Evaluation was performed as follows.

[0352] S: 0.50 mass % or less

[0353] A: more than 0.50 mass % and 1.0 mass % or less

[0354] B: more than 1.0 mass % and 3.0 mass % or less

[0355] C: more than 3.0 mass%

[0356] Comparative Example 1

[0357] In Example 1, the same procedures were performed except that the compound (A) represented by the formula (M1) ("X9-450", manufactured by DIC Corporation) was replaced with an equal amount of a phenylmethane-type maleimide resin (BMI-2300 (trade name), manufactured by Yamato Chemical Industry Co., Ltd.).

[0358] Comparative Example 2

[0359] In Example 1, the same procedures were performed except that the compound (A) represented by formula (M1) ("X9-450", manufactured by DIC Corporation) was replaced with an equal amount of the compound represented by the following structure (BMI-70 (trade name), manufactured by KI Chemical Industry Co., Ltd.).

[0360]

[0361] In the above, Me represents a methyl group and Et represents an ethyl group.

[0362] Example 2

[0363] In Example 1, the same procedures were followed except that the content of the compound (A) represented by the formula (M1) ("X9-450", manufactured by DIC Corporation) was changed to 40 parts by mass and the content of the modified polyphenylene ether obtained in Synthesis Example 1 was changed to 57 parts by mass. The results are shown in Table 1.

[0364] Comparative Example 3

[0365] The same procedures were followed in Example 1 except that the compound (A) represented by the formula (M1) ("X9-450", manufactured by DIC Corporation) was replaced with an equal amount of a maleimide compound (MIR-3000 (trade name), manufactured by Nippon Kayaku Co., Ltd.).

[0366] [Table 1]

[0367]

[0368] Industrial Applicability

[0369] As described above, the resin composition of the present invention can be widely and effectively used as, for example, electrical insulating materials, semiconductor plastic packages, sealing materials, adhesives, laminated materials, anti-corrosion agents, laminated board materials, etc. in various applications such as electrical / electronic materials, machine tool materials, and aviation materials, and can be effectively used as printed circuit board materials for high integration / high density in recent information terminal equipment, communication equipment, etc. In addition, the metal foil-clad laminated board of the present invention has low water absorption, chemical resistance, desmear resistance, and heat resistance, and therefore, its industrial applicability becomes extremely high.

Claims

1. A resin composition comprising: a compound (A) represented by formula (M3), and a compound (B) containing two or more carbon-carbon unsaturated double bonds, Formula (M3) In formula (M3), nx represents an integer of 1 to 20, in, The compound (B) containing two or more carbon-carbon unsaturated double bonds includes a compound represented by formula (1), In formula (1), X represents an aromatic group, -(YO)n2- represents a polyphenylene ether structure, and R 1 , R 2 , and R 3 Each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group, n1 represents an integer of 1 to 6, n2 represents an integer of 1 to 100, and n3 represents an integer of 1 to 4.

2. The resin composition according to claim 1, wherein When the resin solid content in the resin composition is 100 parts by mass, the content of the compound (A) represented by the formula (M3) is 1 to 90 parts by mass.

3. The resin composition according to claim 1 or 2, wherein When the resin solid content in the resin composition is 100 parts by mass, the content of the compound (B) containing two or more carbon-carbon unsaturated double bonds is 1 to 90 parts by mass.

4. A resin composition comprising: a compound (A) represented by formula (M3), and a compound (B) containing two or more carbon-carbon unsaturated double bonds, Formula (M3) In formula (M3), nx represents an integer of 1 to 20, in, The compound (B) containing two or more carbon-carbon unsaturated double bonds comprises: a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds, The resin composition further comprises other resin components (C), and the other resin components (C) are one or more selected from the group consisting of maleimide compounds other than the compound (A) represented by the formula (M3), epoxy compounds, phenolic compounds, oxetane resins, benzoxazine compounds, compounds having polymerizable unsaturated groups other than the compound (B) containing two or more carbon-carbon unsaturated double bonds, and cyanate compounds.

5. A resin composition comprising: a compound (A) represented by formula (M3), and a compound (B) containing two or more carbon-carbon unsaturated double bonds, Formula (M3) In formula (M3), nx represents an integer of 1 to 20, in, The compound (B) containing two or more carbon-carbon unsaturated double bonds comprises: a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds, The resin composition further comprises a filler (D).

6. The resin composition according to claim 5, wherein The content of the filler (D) in the resin composition is 50 to 1600 parts by mass based on 100 parts by mass of the resin solid content.

7. The resin composition according to claim 5, wherein The content of the filler (D) in the resin composition is 30% by mass to 80% by mass of the components excluding the solvent.

8. The resin composition according to claim 1, wherein When the resin solid content in the resin composition is 100 parts by mass, the content of the compound (A) represented by the formula (M3) is 1 to 90 parts by mass, and the content of the compound (B) containing two or more carbon-carbon unsaturated double bonds is 1 to 90 parts by mass, It further comprises other resin components (C), wherein the other resin components (C) are one or more selected from the group consisting of maleimide compounds other than the compound (A) represented by the formula (M3), epoxy compounds, phenolic compounds, oxetane resins, benzoxazine compounds, compounds having polymerizable unsaturated groups other than the compound (B) containing two or more carbon-carbon unsaturated double bonds, and cyanate compounds, It also contains a filling material (D), The content of the filler (D) in the resin composition is 50 to 1600 parts by mass based on 100 parts by mass of the resin solid content.

9. The resin composition according to claim 6 or 7, wherein The compound (B) containing two or more carbon-carbon unsaturated double bonds includes a compound represented by formula (1), In formula (1), X represents an aromatic group, -(YO)n2- represents a polyphenylene ether structure, and R 1 , R 2 , and R 3 Each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group, n1 represents an integer of 1 to 6, n2 represents an integer of 1 to 100, and n3 represents an integer of 1 to 4.

10. The resin composition according to claim 1 or 8, wherein The compound (B) containing two or more carbon-carbon unsaturated double bonds includes a compound represented by formula (2), In formula (2), -(OXO)- is represented by formula (3) and / or formula (4), -(YO)- is represented by formula (5), at least one of a and b represents an integer of 0 to 100 other than 0, and when a and / or b is an integer of 2 or more, two or more -(YO)- are each independently arranged in one structure, or two or more structures are arranged in blocks or randomly. In formula (3), R 4 , R 5 , R 6 , R 10 and R 11 are optionally the same or different, and are an alkyl group or a phenyl group having a carbon number of 6 or less, R 7 , R 8 and R 9 are optionally the same or different and are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, In formula (4), R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 and R 19 are optionally the same or different, and are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, -A- is a linear, branched, or cyclic divalent hydrocarbon group having 20 or less carbon atoms, In formula (5), R 20 , R 21 are optionally the same or different, and are an alkyl group or a phenyl group having a carbon number of 6 or less, R 22 , R 23 They may be the same or different and are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.

11. The resin composition according to claim 1 or 8, which is used for a printed circuit board. 12 . A cured product, which is a cured product of the resin composition according to claim 1 . 13 . A prepreg comprising a base material and the resin composition according to claim 1 . 14 . A metal foil-clad laminate comprising: at least one prepreg according to claim 13 ; and a metal foil disposed on one or both surfaces of the prepreg. 15 . A resin sheet comprising: a support; and a layer formed from the resin composition according to claim 1 and disposed on a surface of the support.

16. A printed circuit board comprising: an insulating layer; and a conductor layer disposed on a surface of the insulating layer. The insulating layer includes at least one of a layer formed from the resin composition according to any one of claims 1 to 11 and a layer formed from the prepreg according to claim 13 .

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