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

Abstract

To provide a resin composition having excellent low water absorption, as well as a cured product, a prepreg, a metal foil-clad laminate, and a printed wiring board.SOLUTION: The resin composition contains a compound (A) represented by Formula (M1) and a compound (B) containing two or more unsaturated carbon-carbon double bonds, and in Formula (M1), A is a four- to six-membered alicyclic group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin composition, a cured product, a prepreg, a metal foil-clad laminate, a resin sheet, and a printed wiring board. [Background technology]

[0002] In recent years, semiconductors used in communication devices, communications equipment, personal computers, etc. have become increasingly highly integrated and miniaturized, and as a result, the properties required of printed wiring boards (e.g., metal foil-clad laminates) used therein are becoming increasingly strict. The main properties required include, for example, metal foil peel strength, low water absorption, desmear resistance, flame resistance, low dielectric constant, low dielectric loss tangent, low thermal expansion coefficient, and heat resistance.

[0003] In order to obtain printed wiring boards with improved properties, resin compositions for use as materials for printed wiring boards have been investigated. For example, Patent Document 1 discloses a resin composition for printed wiring boards that contains (a) a bifunctional vinylbenzyl compound containing a specific polyphenylene ether skeleton, (b) a specific maleimide compound, (c) a specific cyanate ester resin, and (d) a specific epoxy resin.

[0004] Furthermore, Patent Document 2 discloses a resin composition containing a predetermined cyanate ester compound (A), a predetermined polymaleimide compound (B), and a filler (C) as constituent components. Furthermore, Patent Document 3 discloses a resin composition containing a specific polymaleimide compound (A), a modified polyphenylene ether (B) that is terminally modified with a substituent containing a carbon-carbon unsaturated double bond, and a filler (C). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2010-138364 [Patent Document 2] International Publication No. 2016 / 072404 [Patent Document 3] International Publication No. 2019 / 138992 Summary of the Invention [Problem to be solved by the invention]

[0006] As described above, various resin compositions for printed wiring boards have been studied. With recent technological innovations, one of the demands is for resin compositions that are particularly excellent in low water absorption. The present invention aims to solve the above problems by providing a resin composition having excellent low water absorption, as well as a cured product, a prepreg, a metal foil-clad laminate, a resin sheet, and a printed wiring board, and in particular, a resin composition suitable for use in printed wiring boards. [Means for solving the problem]

[0007] As a result of investigations conducted by the present inventors in light of the above problems, the above problems were solved by the following means. <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: Formula (M1) [ka] (In formula (M1), R M1 , R M2 , R M3 , and R M4 R each independently represents a hydrogen atom or an organic group. M5 and R M6 Each of Ar independently represents a hydrogen atom or an alkyl group. M represents a divalent aromatic group. A is a 4- to 6-membered alicyclic group. R M7 and R M8 are each independently an alkyl group. mx is 1 or 2, and lx is 0 or 1. R M9 and R M10R 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, and nx represents an integer of 1 or more and 20 or less. <2> the content of the compound (A) represented by the formula (M1) is 1 to 90 parts by mass when the resin solid content in the resin composition is 100 parts by mass; <1> The resin composition according to claim 1. <3> the content of the compound (B) containing two or more carbon-carbon unsaturated double bonds is 1 to 90 parts by mass when the resin solid content in the resin composition is 100 parts by mass; <1> or <2> The resin composition according to claim 1. <4> Furthermore, the composition further comprises one or more other resin components (C) selected from the group consisting of maleimide compounds other than the compound (A) represented by formula (M1), epoxy compounds, phenol compounds, oxetane resins, benzoxazine compounds, compounds having a polymerizable unsaturated group other than the compound (B) containing two or more carbon-carbon unsaturated double bonds, and cyanate ester compounds. <1> ~ <3> The resin composition according to any one of the above. <5> Further, the filler (D) is contained. <1> ~ <4> The resin composition according to any one of the above. <6> The content of the filler (D) in the resin composition is 50 to 1600 parts by mass per 100 parts by mass of the resin solid content. <5> The resin composition according to claim 1. <7> the compound (B) containing two or more carbon-carbon unsaturated double bonds includes a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds; <1> ~ <6> The resin composition according to any one of the above. <8> The compound (B) containing two or more carbon-carbon unsaturated double bonds includes a compound represented by formula (1): <1> ~ <6> The resin composition according to any one of the above. [ka] (In formula (1), X represents an aromatic group, -(Y-O)n2- represents a polyphenylene ether structure, and R 1 , R 2 , and ,R3 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. <9> For printed wiring boards, <1> ~ <8> The resin composition according to any one of the above. <10> <1> ~ <9> A cured product of the resin composition according to any one of the above. <11> A substrate; <1> ~ <9> A prepreg formed from the resin composition according to any one of the above items. <12> At least one <11> and a metal foil arranged on one or both sides of the prepreg. <13> a support and a substrate disposed on the surface of the support <1> ~ <9> A resin sheet comprising a layer formed from the resin composition according to any one of the above items. <14> A printed wiring board including an insulating layer and a conductor layer disposed on a surface of the insulating layer, wherein the insulating layer: <1> ~ <9> A layer formed from the resin composition according to any one of <11> A printed wiring board comprising at least one layer formed from the prepreg according to claim 1. [Effects of the Invention]

[0008] The present invention makes it possible to provide a resin composition having excellent low water absorption, as well as a cured product, a prepreg, a metal foil-clad laminate, a resin sheet, and a printed wiring board. In particular, it makes it possible to provide a resin composition suitable for printed wiring board applications. DETAILED DESCRIPTION OF THE INVENTION

[0009] Hereinafter, an embodiment for carrying out the present invention (hereinafter simply referred to as "the present embodiment") will be described in detail. Note that the present embodiment is an example for explaining the present invention, and the present invention is not limited to only this embodiment. In this specification, the symbol "to" is used to mean that the numerical values ​​before and after it are included as the lower limit and upper limit. In this specification, various physical properties and characteristic values ​​are those at 23°C unless otherwise specified. In the description of groups (atomic groups) in this specification, when a notation does not specify whether they are substituted or unsubstituted, it includes both groups (atomic groups) that have no substituents and groups (atomic groups) that have substituents. For example, the term "alkyl group" includes not only alkyl groups that have no substituents (unsubstituted alkyl groups) but also alkyl groups that have substituents (substituted alkyl groups). In this specification, when a notation does not specify whether they are substituted or unsubstituted, it is preferable that they be unsubstituted. In this specification, "parts by mass" indicates the relative amount of a component, and "% by mass" indicates the absolute amount of a component.

[0010] In this specification, the resin solids content refers to components excluding fillers and solvents, and is intended to include the compound (A) represented by formula (M1), the compound (B) containing two or more carbon-carbon unsaturated double bonds, as well as other resin components (C) that are blended as necessary, elastomers, silane coupling agents, and other components (additives such as flame retardants, etc.).

[0011] The resin composition of this 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. [ka] (In formula (M1), R M1 , R M2 , R M3 , and R M4 R each independently represents a hydrogen atom or an organic group. M5 and R M6 Each of Ar independently represents a hydrogen atom or an alkyl group. M represents a divalent aromatic group. A is a 4- to 6-membered alicyclic group. R M7 and R M8 are each independently an alkyl group. mx is 1 or 2, and lx is 0 or 1. R M9 and R M10 R 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, and nx represents an integer of 1 or more and 20 or less.

[0012] By using such a resin composition, a cured resin composition having excellent low water absorption properties can be obtained, and the resin composition can be preferably used as a material for printed wiring boards. The reason why the cured product of the resin composition of this embodiment has excellent low water absorption is not limited, but is presumed to be as follows. Specifically, in this embodiment, by using a compound (compound represented by formula (M1)) having two maleimide groups and a fused ring of an alicyclic ring, such as an indane ring, with an aromatic ring, a cyclic aliphatic group can be introduced into the cured product, and it is presumed that a cured product of the resin composition having low water absorption and excellent dielectric properties (low dielectric constant (Dk) and / or low dielectric dissipation factor (Df)) can be obtained. Meanwhile, the aromatic portion of the fused ring of an alicyclic ring, such as an indane ring, with an aromatic ring maintains good heat resistance, increasing the applicability for printed wiring board applications. Furthermore, the combined use of a compound (B) containing two or more carbon-carbon unsaturated double bonds improves the dielectric properties. Specifically, this embodiment is highly valuable in that it achieves low water absorption while maintaining the dielectric properties required for printed wiring boards.

[0013] <Compound (A) represented by formula (M1)> The resin composition of this embodiment contains a compound (A) represented by formula (M1). Because the compound represented by formula (M1) contains two maleimide groups per molecule, the compounds (A) represented by formula (M1) react with each other, and also react with a compound (B) containing two or more carbon-carbon unsaturated double bonds, and further react with other curable resin components (e.g., the "other resin component (C)" described below) to form a cured product. This, along with the cured product of the compound (B) containing two or more carbon-carbon unsaturated double bonds, forms a cured product. Additionally, by employing the compound (A) represented by formula (M1), the distance between the maleimide groups (the distance between crosslinking points) is optimized. Therefore, in the resin composition of this embodiment, the fused ring structure of an alicyclic ring and an aromatic ring, such as an indane ring, contained in the compound (A) represented by formula (M1) is positioned at an appropriate distance within the cured product, thereby achieving low water absorption. Furthermore, by using the compound (A) represented by formula (M1) in combination with the compound (B) containing two or more carbon-carbon unsaturated double bonds, excellent dielectric properties can be achieved. Furthermore, the cured product of the resin composition of this embodiment contains the compound (A) represented by formula (M1), and therefore can maintain good dielectric properties even after absorbing moisture. Generally, the dielectric properties of cured products of this type of resin composition deteriorate when they absorb moisture. However, because the A portion of the compound (A) represented by formula (M1) has an alicyclic structure, the polarity of the compound is reduced, making it less likely to attract water.

[0014] The compound represented by formula (M1) will be described below. [ka] (In formula (M1), R M1 , R M2 , R M3 , and R M4 R each independently represents a hydrogen atom or an organic group. M5 and R M6 Each of Ar independently represents a hydrogen atom or an alkyl group. M represents a divalent aromatic group. A is a 4- to 6-membered alicyclic group. R M7 and RM8 are each independently an alkyl group. mx is 1 or 2, and lx is 0 or 1. R M9 and R M10 R 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, and nx represents an integer of 1 or more and 20 or less.

[0015] R in the formula M1 , R M2 , R M3 , and R M4 R 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, even more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, with a methyl group being particularly preferred. M1 and R M3 are each independently preferably an alkyl group, and R M2 and R M4 is preferably a hydrogen atom. R M5 and R M6 are each independently a hydrogen atom or an alkyl group, preferably an alkyl group. The alkyl group here 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. Ar M represents a divalent aromatic group, preferably a phenylene group, a naphthalenediyl group, a phenanthrenediyl group, or an anthracenediyl group, more preferably a phenylene group, and even more preferably an m-phenylene group. M may have a substituent, and the substituent is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, even more preferably an alkyl group having 1 to 6 carbon atoms, still more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group. Mis preferably unsubstituted. A is a 4- to 6-membered alicyclic group, and more preferably a 5-membered alicyclic group (preferably a group that forms an indane ring when combined with a benzene ring). M7 and R M8 are each 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. R M9 and R M10 are each independently a hydrogen atom or an alkyl group, preferably an alkyl group. The alkyl group here 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. R M11 , R M12 , R M13 , and R M14 R 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, even more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, with a methyl group being particularly preferred. M12 and R M13 are each independently preferably an alkyl group, and R M11 and R M14 is preferably a hydrogen atom. nx represents an integer of 1 or more and 20 or less. nx may be an integer of 10 or less. The resin composition of this embodiment may contain only one compound (A) represented by formula (M1) having at least one different value of nx, or may contain two or more. When two or more compounds are contained, the average value of nx (average number of repeating units) n in the compound (A) represented by formula (M1) in the resin composition is preferably 0.95 or more, more preferably 0.98 or more, even more preferably 1.0 or more, and even more preferably 1.1 or more, in order to achieve a low melting point (low softening point), low melt viscosity, and excellent handleability. The same applies to formulas (M2) and (M3) described below.

[0016] The compound represented by formula (M1) is preferably a compound represented by the following formula (M2). [ka] (In formula (M2), R M21 , R M22 , R M23 , and R M24 R each independently represents a hydrogen atom or an organic group. M25 and R M26 R each independently represents a hydrogen atom or an alkyl group. M27 , R M28 , R M29 , and R M30 R each independently represents a hydrogen atom or an organic group. M31 and R M32 R each independently represents a hydrogen atom or an alkyl group. M33 , R M34 , R M35 , and R M36 R 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, and nx represents an integer of 1 or more and 20 or less.

[0017] R in the formula M21 , R M22 , R M23 , and R M24 R 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, even more preferably an alkyl group having 1 to 6 carbon atoms, still more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group. M21 and R M23 is preferably an alkyl group, and R M22 and R M24 is preferably a hydrogen atom. R M25 and R M26 are each independently a hydrogen atom or an alkyl group, preferably an alkyl group. The alkyl group here 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. 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, even more preferably an alkyl group having 1 to 6 carbon atoms, still more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group. R M31 and R M32 are each independently a hydrogen atom or an alkyl group, preferably an alkyl group. The alkyl group here 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. R M33 , R M34 , R M35 , and R M36each 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, even more preferably an alkyl group having 1 to 6 carbon atoms, still more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and particularly preferably a methyl group. R M33 and R M36 is preferably a hydrogen atom, and R M34 and R M35 is preferably an alkyl group. R M37 , R M38 , R M39 are each independently a hydrogen atom or an alkyl group, preferably an alkyl group. The alkyl group here 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. nx represents an integer of 1 or more and 20 or less. nx may be an integer of 10 or less.

[0018] The compound represented by formula (M2) is preferably a compound represented by the following formula (M3). [ka] (In formula (M3), nx represents an integer of 1 or more and 20 or less.) nx may be an integer of 10 or less.

[0019] The molecular weight of the compound (A) represented by formula (M1) is preferably 500 or more, more preferably 600 or more, and even more preferably 700 or more. By making the molecular weight equal to or greater than the lower limit, the dielectric properties (low dielectric property) and low water absorption of the resulting cured product tend to be further improved. Furthermore, the molecular weight of the compound (A) represented by formula (M1) is preferably 10,000 or less, more preferably 9,000 or less, even more preferably 7,000 or less, even more preferably 5,000 or less, and even more preferably 4,000 or less. By making the molecular weight equal to or less than the upper limit, the heat resistance and handleability of the resulting cured product tend to be further improved.

[0020] Furthermore, it is preferable that the compound (A) used in this embodiment and represented by formula (M1) has excellent dielectric properties when cured. For example, the cured product of the compound (A) used in this embodiment and represented by formula (M1) preferably has a dielectric constant (Dk) of 3.0 or less, more preferably 2.6 or less, measured according to the cavity resonance perturbation method. Furthermore, a practical lower limit for the dielectric constant is, for example, 2.0 or more. Furthermore, the cured product of the compound (A) used in this embodiment and represented by formula (M1) preferably has a dielectric loss tangent (Df) of 0.01 or less, more preferably 0.007 or less, measured according to the cavity resonance perturbation method. Furthermore, a practical lower limit for the dielectric loss tangent is, for example, 0.0001 or more.

[0021] Furthermore, the compound (A) used in this embodiment and represented by formula (M1) preferably has high heat resistance when cured. The cured product of the compound (A) used in this embodiment and represented by formula (M1) preferably has a glass transition temperature of 180°C or higher, more preferably 200°C or higher, and even more preferably 230°C or higher, as measured in accordance with JIS C6481:1996 Dynamic Viscoelasticity Measurement. By setting the glass transition temperature at or above the lower limit, a cured product with even better heat resistance can be obtained. Furthermore, it is practical for the upper limit of the glass transition temperature to be 400°C or lower. As the compound (A) represented by formula (M1) used in this embodiment, for example, X9-450 and X9-470 manufactured by DIC Corporation can be used.

[0022] In the resin composition of this embodiment, the content of the compound (A) represented by formula (M1) is preferably 1 to 90 parts by mass, based on 100 parts by mass of the resin solid content in the resin composition. The lower limit of the content of the compound (A) represented by formula (M1), based on 100 parts by mass of the resin solid content in the resin composition, is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, even more preferably 20 parts by mass or more, even more preferably 30 parts by mass or more, even more preferably 40 parts by mass or more, and may be 60 parts by mass or more, or even 70 parts by mass or more. By setting the content at or above the lower limit, the heat resistance of the resulting cured product tends to be further improved. Furthermore, the upper limit of the content of the compound (A) represented by formula (M1), based on 100 parts by mass of the resin solid content in the resin composition, is preferably 88 parts by mass or less, more preferably 85 parts by mass or less, even more preferably 83 parts by mass or less, even more preferably 80 parts by mass or less, and may be 79 parts by mass or less. By adjusting the content to the above upper limit or less, the low water absorbency of the obtained cured product tends to be further improved.

[0023] Furthermore, in the resin composition of this embodiment, the content of the compound (A) represented by formula (M1) is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, even more preferably 30% by mass or more, even more preferably 40% by mass or more, and may be 60% by mass or more, or even 70% by mass or more, based on the total amount of resin solids. By setting the content at or above the lower limit, the heat resistance of the resulting cured product tends to be further improved. Furthermore, the upper limit of the content of the compound (A) represented by formula (M1) is preferably 88% by mass or less, more preferably 85% by mass or less, even more preferably 83% by mass or less, even more preferably 80% by mass or less, and may be 79% by mass or less, based on the total amount of resin solids in the resin composition. By setting the content at or below the upper limit, the low water absorption of the resulting cured product tends to be further improved. The resin composition of the present embodiment may contain only one compound (A) represented by formula (M1), or may contain two or more compounds. When two or more compounds are contained, the total amount is preferably in the above range.

[0024] <Compound (B) containing two or more carbon-carbon unsaturated double bonds> The resin composition of this embodiment contains a compound (B) containing two or more carbon-carbon unsaturated double bonds. In this embodiment, by using the compound (A) represented by formula (M1) in combination with the compound (B) containing two or more carbon-carbon unsaturated double bonds, it is possible to achieve more excellent dielectric properties than when a conventionally used maleimide compound is used in combination with the compound (B) containing two or more carbon-carbon unsaturated double bonds. The carbon-carbon unsaturated double bond contained in the compound (B) containing two or more carbon-carbon unsaturated double bonds used in this embodiment is a polymerizable unsaturated group, and is usually a carbon-carbon unsaturated double bond that reacts with some 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, or the like.

[0025] As the compound (B) containing two or more carbon-carbon unsaturated double bonds used in this embodiment, a wide range of compounds containing two or more carbon-carbon unsaturated double bonds that are commonly used in printed wiring boards can be used. Specifically, the upper limit for the number of carbon-carbon unsaturated double bonds contained in the compound (B) containing two or more carbon-carbon unsaturated double bonds used in this embodiment is preferably 10 or less, more preferably 5 or less, and even more preferably 2. By ensuring that the number is equal to or less than the upper limit, the heat resistance of the obtained cured product and the handleability of the resin composition tend to be further improved. Furthermore, the compound (B) containing two or more carbon-carbon unsaturated double bonds used in this embodiment preferably has excellent dielectric properties when cured. For example, the cured product of the compound (B) containing two or more carbon-carbon unsaturated double bonds used in this embodiment preferably has a dielectric constant (Dk) of 3.0 or less, more preferably 2.6 or less, measured according to the cavity resonance perturbation method. Furthermore, a practical lower limit for the dielectric constant is, for example, 2.0 or more. Furthermore, the cured product of the compound (B) containing two or more carbon-carbon unsaturated double bonds used in this embodiment preferably has a dielectric loss tangent (Df) of 0.01 or less, more preferably 0.007 or less, measured according to the cavity resonance perturbation method. Furthermore, a practical lower limit for the dielectric loss tangent is, for example, 0.0001 or more.

[0026] Furthermore, the compound (B) containing two or more carbon-carbon unsaturated double bonds used in this embodiment preferably has high heat resistance when cured. The cured product of the compound (B) containing two or more carbon-carbon unsaturated double bonds used in this embodiment preferably has a glass transition temperature of 150°C or higher, more preferably 180°C or higher, and even more preferably 200°C or higher, as measured in accordance with JIS C6481 dynamic viscoelasticity measurement. By setting the glass transition temperature at or above the lower limit, a cured product with excellent heat resistance can be obtained. Furthermore, it is practical for the upper limit of the glass transition temperature to be 400°C or lower.

[0027] The compound (B) containing two or more carbon-carbon unsaturated double bonds preferably has a number average molecular weight of 500 or more, more preferably 1000 or more, even more preferably 1200 or more, even more preferably 1500 or more, and may even be 1800 or more, as measured by GPC in terms of polystyrene. By setting the number average molecular weight at or above the lower limit, the low dielectric properties of the resulting cured product tend to be further improved. Furthermore, the number average molecular weight of the compound (B) containing two or more carbon-carbon unsaturated double bonds is preferably 7000 or less, more preferably 5000 or less, even more preferably 3500 or less, even more preferably 3000 or less, and even more preferably 2300 or less. By setting the number average molecular weight at or below the upper limit, the heat resistance of the resulting cured product tends to be further improved.

[0028] The compound (B) containing two or more carbon-carbon unsaturated double bonds used in this embodiment preferably contains a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds. Furthermore, it is preferred that 90 mass % or more (more preferably 95 mass % or more, and even more preferably 99 mass % or more) of the compound (B) containing two or more carbon-carbon unsaturated double bonds contained in the resin composition of this embodiment be a polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds. 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. These will be explained in detail below.

[0029] The polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds is exemplified by a compound having a phenylene ether skeleton represented by the following formula (X1).

[0030] [ka] (In formula (X1), R 24 , R 25 , R 26 , and ,R 27may be the same or different and represent an alkyl group having 6 or less carbon atoms, an aryl group, a halogen atom, or a hydrogen atom.

[0031] The polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds has the formula (X2): [ka] (In formula (X2), R 28 , R 29 , R 30 , R 34 , and ,R 35 may be the same or different and represent an alkyl group having 6 or less carbon atoms or a phenyl group. 31 , R 32 , and ,R 33 may be the same or different and are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. and / or a repeating unit represented by formula (X3): [ka] (In formula (X3), R 36 , R 37 , R 38 , R 39 , R 40 , R 41 , R 42 , and ,R 43 may be 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.

[0032] The polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds is preferably a modified polyphenylene ether compound in which some or all of the terminals are functionalized with ethylenically unsaturated groups (hereinafter, sometimes referred to as "modified polyphenylene ether compound (g)"), and more preferably a modified polyphenylene ether compound having a vinylbenzyl group at the terminal. By using such a modified polyphenylene ether compound (g), it is possible to further reduce the dielectric loss tangent (Df) of the cured product of the resin composition and increase the metal foil peel strength. These compounds may be used alone or in combination of two or more.

[0033] The method for producing a modified polyphenylene ether compound is not particularly limited as long as it can achieve the effects of the present invention. For example, a compound functionalized with an ethylenically unsaturated group (specifically, a vinylbenzyl group, etc.) can be produced by dissolving a bifunctional phenylene ether oligomer and vinylbenzyl chloride in a solvent, adding a base under heating and stirring to cause a reaction, and then solidifying the resin. A compound functionalized with a carboxy group can be produced, for example, by melt-kneading a polyphenylene ether compound with an unsaturated carboxylic acid or a functionalized derivative thereof in the presence or absence of a radical initiator, and then reacting the compound. Alternatively, a compound can be produced by dissolving a polyphenylene ether compound with an unsaturated carboxylic acid or a functionalized derivative thereof in an organic solvent in the presence or absence of a radical initiator, and then reacting the compound in solution.

[0034] Examples of the ethylenically unsaturated groups contained in the modified polyphenylene ether compound (g) include alkenyl groups such as ethenyl, allyl, acryloyl, methacryloyl, propenyl, butenyl, hexenyl, and octenyl; cyclic alkenyl groups such as cyclopentenyl and cyclohexenyl; and alkenylaryl groups such as vinylbenzyl and vinylnaphthyl. Vinylbenzyl is preferred. When the modified polyphenylene ether compound (g) has two or more ethylenically unsaturated groups, the two or more ethylenically unsaturated groups may be the same or different functional groups. The use of such modified polyphenylene ether compounds can reduce the dielectric loss tangent (Df) of the cured resin composition and increase the metal foil peel strength.

[0035] The modified polyphenylene ether compound (g) includes a compound represented by formula (1). [ka] (In formula (1), X represents an aromatic group, -(Y-O)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. When n2 and / or n3 are integers of 2 or more, the n2 structural units (Y-O) and / or the n3 structural units may be the same or different. n3 is preferably 2 or more, and more preferably 2.

[0036] The modified polyphenylene ether compound (g) in this embodiment is preferably represented by formula (2). [ka] where -(OXO)- is a compound represented by formula (3): [ka] (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 or a phenyl group having 6 or less carbon atoms. 7 , R 8 , and ,R 9 may be the same or different and are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. and / or formula (4): [ka] (In formula (4), R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , and ,R 19 may be 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.

[0037] Also, -(YO)- is a group represented by the formula (5): [ka] (In formula (5), R 20 , R 21 R may be the same or different and is an alkyl group or a phenyl group having 6 or less carbon atoms. 22 , R 23 may be the same or different and are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. In formula (2), a and b, at least one of which is not 0, represent an integer of 0 to 100, preferably an integer of 0 to 50, and more preferably an integer of 1 to 30. When a and / or b are an integer of 2 or greater, two or more -(YO)- groups may each independently represent an arrangement of one type of structure, or two or more types of structures may be arranged in blocks or randomly.

[0038] 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), 1,3-phenylenebis(1-methylethylidene), cyclohexylidene, phenylmethylene, naphthylmethylene, and 1-phenylethylidene.

[0039] Among the modified polyphenylene ether compounds (g), R 4 , R 5 , R 6 , R 10 , R 11 , R 20 , and ,R 21 is an alkyl group having 3 or less carbon atoms, and 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 23is 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 are integers of 2 or more, the two or more -(YO)- may each independently be 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.

[0040] [ka] [ka] (In formula (10), R 44 , R 45 , R 46 , and ,R 47 may be the same or different and are a hydrogen atom or a methyl group. -B- is a linear, branched, or cyclic divalent hydrocarbon group having 20 or less carbon atoms. Specific examples of -B- include the same as the specific examples of -A- in formula (4). [ka] (In formula (11), -B- is a linear, branched, or cyclic divalent hydrocarbon group having 20 or less carbon atoms.) Specific examples of -B- include the same as the specific examples of -A- in formula (4). [ka] [ka]

[0041] The preparation method (production method) of the modified polyphenylene ether compound (g) represented by formula (2) is not particularly limited, and can be produced, for example, by a step of oxidatively coupling a bifunctional phenol compound with a monofunctional phenol compound to obtain a bifunctional phenylene ether oligomer (oxidative coupling step), and a step of vinylbenzyl-etherifying the terminal phenolic hydroxyl groups of the obtained bifunctional phenylene ether oligomer (vinylbenzyl-etherification step). In addition, as such a modified polyphenylene ether compound, for example, a product manufactured by Mitsubishi Gas Chemical Company, Inc. (OPE-2St1200, etc.) can be used.

[0042] In the oxidative coupling step, for example, a difunctional phenylene ether oligomer can be obtained by dissolving a difunctional phenolic compound, a monofunctional phenolic compound, and a catalyst in a solvent and then blowing oxygen into the solution while heating and stirring. The difunctional phenolic 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 phenolic 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, CuCl, CuBr, etc.), amines (e.g., di-n-butylamine, n-butyldimethylamine, N,N'-di-t-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.

[0043] In the vinylbenzyl etherification step, for example, the bifunctional phenylene ether oligomer obtained in the oxidative coupling step and vinylbenzyl chloride are dissolved in a solvent, a base is added under heating and stirring to cause a reaction, and the resulting resin is solidified. The vinylbenzyl chloride is not particularly limited, and examples thereof include at least one selected from the group consisting of o-vinylbenzyl chloride, m-vinylbenzyl chloride, and p-vinylbenzyl chloride. The base is not particularly limited, and examples thereof include at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium methoxide, and sodium ethoxide. In the vinylbenzyl etherification step, an acid may be used to neutralize the base remaining after the reaction. The acid is not particularly limited, and examples thereof include at least one selected from the group consisting of hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, and nitric acid. The solvent is not particularly limited and may be, for example, at least one selected from the group consisting of toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, methylene chloride, and chloroform. Methods for solidifying the resin include, for example, evaporating the solvent to dryness, and mixing the reaction solution with a poor solvent and reprecipitation.

[0044] In addition to the above, the polyphenylene ether compound used in this embodiment may be an unmodified polyphenylene ether compound having a terminal hydroxyl group. As the unmodified polyphenylene ether compound, for example, the description in paragraphs 0011 to 0016 of JP 2017-119739 A can be used, the contents of which are incorporated herein by reference.

[0045] The polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds (preferably a modified polyphenylene ether compound (g)) preferably has a polystyrene-equivalent number average molecular weight of 500 or more and 3000 or less, as determined by a GPC (gel permeation chromatography) method. When the number average molecular weight is 500 or more, stickiness tends to be further suppressed when the resin composition of the present embodiment is formed into a coating film. When the number average molecular weight is 3000 or less, solubility in solvents tends to be further improved. Furthermore, the weight average molecular weight of the polystyrene-equivalent polyphenylene ether compound containing two or more carbon-carbon unsaturated double bonds (preferably the modified polyphenylene ether compound (g)) measured by GPC is preferably from 800 to 10,000, and more preferably from 800 to 5,000. By setting the weight average molecular weight at or above the lower limit, the dielectric constant (Dk) and dielectric loss tangent (Df) of the cured product of the resin composition tend to be lower, while by setting the weight average molecular weight at or below the upper limit, the solubility, low viscosity, and moldability of the resin composition in solvents when preparing a varnish or the like, which will be described later, tend to be improved. Furthermore, in the case of the modified polyphenylene ether compound (g), the terminal carbon-carbon unsaturated double bond equivalent is preferably 400 to 5000 g per carbon-carbon unsaturated double bond, more preferably 400 to 2500 g. By setting the equivalent at or above the lower limit, the dielectric constant (Dk) and dielectric loss tangent (Df) of the cured product of the resin composition tend to be lower. By setting the equivalent at or below the upper limit, the solubility, low viscosity, and moldability of the resin composition in solvents tend to be improved.

[0046] In the resin composition of this embodiment, the content of the compound (B) containing two or more carbon-carbon unsaturated double bonds is preferably 1 to 90 parts by mass, based on 100 parts by mass of the resin solid content in the resin composition. The lower limit of the content of the compound (B) containing two or more carbon-carbon unsaturated double bonds, based on 100 parts by mass of the resin solid content in the resin composition, is preferably 3 parts by mass or more, more preferably 7 parts by mass or more, even more preferably 12 parts by mass or more, even more preferably 15 parts by mass or more, and even more preferably 18 parts by mass or more. By ensuring that the content is equal to or greater than the lower limit, the low water absorption and dielectric properties (Dk and / or Df) of the resulting cured product tend to be further improved. Furthermore, the upper limit of the content of compound (B) containing two or more carbon-carbon unsaturated double bonds is preferably 80 parts by mass or less, more preferably 70 parts by mass or less, even more preferably 60 parts by mass or less, even more preferably 50 parts by mass or less, and even more preferably 40 parts by mass or less, and may be 30 parts by mass or less, or 25 parts by mass or less, relative to 100 parts by mass of the resin solid content in the resin composition. By keeping the content below the upper limit, the heat resistance and chemical resistance of the obtained cured product tend to be further improved.

[0047] Furthermore, in the resin composition of this embodiment, the content of the compound (B) containing two or more carbon-carbon unsaturated double bonds is preferably 3% by mass or more, more preferably 7% by mass or more, even more preferably 12% by mass or more, even more preferably 15% by mass or more, and even more preferably 18% by mass or more, based on the resin solids. By setting the content at or above the lower limit, the low water absorption and dielectric properties (Dk and / or Df) of the resulting cured product tend to be further improved. Furthermore, the upper limit of the content of the compound (B) containing two or more carbon-carbon unsaturated double bonds is preferably 80% by mass or less, more preferably 70% by mass or less, even more preferably 60% by mass or less, even more preferably 50% by mass or less, even more preferably 40% by mass or less, and may be 30% by mass or less, or even 25% by mass or less, based on the resin solids in the resin composition. By setting the content at or below the upper limit, the heat resistance and chemical resistance of the resulting cured product tend to be further improved. 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. When two or more compounds are contained, the total amount is preferably in the above range.

[0048] In the resin composition of this embodiment, the total amount of the compound (A) represented by formula (M1) and the compound (B) containing two or more carbon-carbon unsaturated double bonds is preferably 20% by mass or more of the resin solids, more preferably 30% by mass or more, even more preferably 40% by mass or more, even more preferably 50% by mass or more, even more preferably 60% by mass or more, even more preferably 70% by mass or more, and may even be 80% by mass or more, 90% by mass or more, or 95% by mass or more. By adjusting the total amount to be equal to or greater than the above-mentioned lower limit, the heat resistance, low water absorbency, and dielectric properties of the resulting cured product tend to be further improved. Furthermore, the upper limit of the total amount is preferably equal to or less than 99.9% by mass, more preferably equal to or less than 99% by mass, of the resin solids in the resin composition. By adjusting the total amount to be equal to or less than the above-mentioned upper limit, the heat resistance, low water absorbency, and dielectric properties of the resulting cured product tend to be further improved.

[0049] In the resin composition of this embodiment, the mass ratio of the compound (A) represented by 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, even more preferably 4.5:1 to 1.5:1, and still more preferably 4:1 to 2:1. With such a blend ratio, condensed rings of an alicyclic ring and an aromatic ring, such as an indan ring, contained in the compound (A) represented by formula (M1) are present at an appropriate distance in the cured product, making it possible to improve the relatively low water absorbency.

[0050] <Other resin components (C)> The resin composition of this embodiment may further include one or more other resin components (C) selected from the group consisting of maleimide compounds other than the compound (A) represented by formula (M1), epoxy compounds, phenolic compounds, oxetane resins, benzoxazine compounds, compounds having a polymerizable unsaturated group other than the compound (B) containing two or more carbon-carbon unsaturated double bonds, and cyanate ester compounds. Preferably, the resin composition includes one or more other components selected from the group consisting of maleimide compounds other than the compound (A) represented by formula (M1), epoxy compounds, phenolic compounds, oxetane resins, benzoxazine compounds, and compounds having a polymerizable unsaturated group other than the compound (B) containing two or more carbon-carbon unsaturated double bonds. The inclusion of such components allows the printed wiring board to more effectively exhibit other desired performance characteristics. In this embodiment, the resin composition preferably includes a maleimide compound and an epoxy compound, and more preferably includes an epoxy compound.

[0051] It is preferable that the cured product of each of the other resin components (C) has excellent dielectric properties. For example, the dielectric constant (Dk) of the cured product of each of the other resin components (C), measured according to the cavity resonance perturbation method, is preferably 4.0 or less, more preferably 3.5 or less. Furthermore, a practical lower limit for the dielectric constant (Dk) is, for example, 2.0 or more. Furthermore, it is preferable that the dielectric loss tangent (Df) of the cured product of each of the other resin components (C), measured according to the cavity resonance perturbation method, is 0.03 or less, more preferably 0.002 or less. Furthermore, a practical lower limit for the dielectric loss tangent (Df) is, for example, 0.0001 or more.

[0052] Furthermore, it is preferable that the other resin component (C) has high heat resistance when cured. For example, the glass transition temperature of the cured product of each of the other resin components (C), measured according to JIS C6481 dynamic viscoelasticity measurement, is preferably 150°C or higher, more preferably 180°C or higher, and even more preferably 200°C or higher. By setting the glass transition temperature at or above the lower limit, a cured product with even better heat resistance can be obtained. Furthermore, it is practical for the upper limit of the glass transition temperature to be 400°C or lower.

[0053] The resin composition of the present embodiment may also contain an elastomer. Furthermore, the resin composition of the present embodiment may also contain a silane coupling agent. Furthermore, the resin composition of the present embodiment may also contain an active ester compound. Furthermore, the resin composition of the present embodiment may also contain additives that are commonly used in the technical field of the present invention, as long as they do not deviate from the spirit of the present invention. The other resin component (C), as well as the elastomer, silane coupling agent, and active ester will be described in detail below.

[0054] <<Maleimide Compounds Other than Compound (A) Represented by Formula (M1)>> The resin composition of the present embodiment may contain a maleimide compound other than the compound (A) represented by formula (M1) (hereinafter, sometimes simply referred to as "another maleimide compound"). The other maleimide compound is not particularly limited as long as it is a compound having one or more (preferably 2 to 12, more preferably 2 to 6, even more preferably 2 to 4, still more preferably 2 or 3, and even more 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. Examples of other maleimide compounds include compounds represented by formulas (2M) to (4M). When these other maleimide compounds are used in materials for printed wiring boards (e.g., laminates, metal foil-clad laminates), they can impart excellent heat resistance. [ka] In formula (2M), R 54 each independently represents a hydrogen atom or a methyl group, and n4 represents an integer of 1 or greater. n4 is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, even more preferably an integer of 1 to 3, and still more preferably 1 or 2. [ka] 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 or more and 10 or less. R 55 is preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, or a phenyl group, more preferably one of a hydrogen atom and a methyl group, and even more preferably a hydrogen atom. n5 is preferably an integer of 1 or more and 5 or less, more preferably an integer of 1 to 3, and even more preferably 1 or 2. [ka] 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.

[0055] Among the compounds represented by the formulae (2M) to (4M), the compound represented by the formula (3M) is more preferred. Other maleimide compounds may be prepared by known methods, or commercially available products may be used, such as "MIR-3000" manufactured by Nippon Kayaku Co., Ltd. as a compound represented by formula (3M), "BMI-2300" manufactured by Daiwa Kasei Kogyo Co., Ltd. as a compound represented by formula (2M), and "BMI-70" manufactured by K.I. Kasei Co., Ltd. as a compound represented by formula (4M).

[0056] Furthermore, examples of other maleimide compounds besides those mentioned above include phenylmethane maleimide oligomers, m-phenylene bismaleimide, 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane, 4-methyl-1,3-phenylene bismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 4,4'-diphenylether bismaleimide, 4,4'-diphenylsulfone bismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene, prepolymers thereof, and prepolymers of these maleimides and amines.

[0057] When the resin composition of this embodiment contains another maleimide compound, the lower limit of the content of the other maleimide compound is preferably 1 part by mass or more, more preferably 10 parts by mass or more, and may even be 15 parts by mass or more, per 100 parts by mass of the resin solid content in the resin composition. Having the content of the other maleimide compound at 1 part by mass or more tends to improve the flame resistance of the resulting cured product. When the resin composition of this embodiment contains another maleimide compound, the upper limit of the content of the other maleimide compound is preferably 70 parts by mass or less, more preferably 50 parts by mass or less, even more preferably 30 parts by mass or less, and even more preferably 20 parts by mass or less, per 100 parts by mass of the resin solid content in the resin composition. Having the content of the other maleimide compound at 70 parts by mass or less tends to improve the metal foil peel strength and low water absorbency. The resin composition of the present embodiment may contain only one type of other maleimide compound, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range. The resin composition of the present embodiment may also be configured to be substantially free of other maleimide compounds, meaning that the content of other maleimide compounds is less than 1 part by mass per 100 parts by mass of the resin solid content in the resin composition.

[0058] <<Epoxy compounds>> The resin composition of the present embodiment may contain an epoxy compound. 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, even more preferably 2 to 4, even more preferably 2 or 3, and even more 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. Examples of epoxy compounds include bisphenol A epoxy resins, bisphenol E epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, phenol novolac epoxy resins, bisphenol A novolac epoxy resins, glycidyl ester epoxy resins, aralkyl novolac epoxy resins, biphenyl aralkyl epoxy resins, naphthylene ether epoxy resins, cresol novolac epoxy resins, multifunctional phenol epoxy resins, naphthalene epoxy resins, anthracene epoxy resins, naphthalene skeleton-modified novolac epoxy resins, phenol aralkyl epoxy resins, naphthol aralkyl epoxy resins, dicyclopentadiene epoxy resins, biphenyl epoxy resins, alicyclic epoxy resins, polyol epoxy resins, phosphorus-containing epoxy resins, glycidyl amines, glycidyl esters, compounds in which the double bond of butadiene or the like has been epoxidized, and compounds obtained by reacting hydroxyl group-containing silicone resins with epichlorohydrin. The use of these compounds improves the moldability and adhesion of the resin composition. Among these, from the viewpoint of further improving flame retardancy and heat resistance, biphenyl aralkyl type epoxy resins, naphthylene ether type epoxy resins, polyfunctional phenol type epoxy resins, and naphthalene type epoxy resins are preferred, and biphenyl aralkyl type epoxy resins are more preferred.

[0059] The resin composition of this embodiment preferably contains an epoxy compound within a range that does not impair the effects of the present invention. When the resin composition of this embodiment contains an epoxy compound, the content thereof is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 2 parts by mass or more, per 100 parts by mass of the resin solid content in the resin composition. When the epoxy compound content is 0.1 parts by mass or more, the metal foil peel strength and toughness tend to be improved. When the resin composition of this embodiment contains an epoxy compound, the upper limit of the epoxy compound content is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, even more preferably 8 parts by mass or less, and even more preferably 5 parts by mass or less, per 100 parts by mass of the resin solid content in the resin composition. When the epoxy compound content is 50 parts by mass or less, the electrical properties of the resulting cured product tend to be improved. The resin composition in the present embodiment may contain only one type of epoxy compound, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

[0060] <<Phenol compounds>> The resin composition of the present embodiment may contain a phenol compound. The phenol compound is not particularly limited as long as it has one or more (preferably 2 to 12, more preferably 2 to 6, even more preferably 2 to 4, even more preferably 2 or 3, and even more 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. Examples of the phenol compound include bisphenol A type phenolic resins, bisphenol E type phenolic resins, bisphenol F type phenolic resins, bisphenol S type phenolic resins, phenol novolac resins, bisphenol A novolac type phenolic resins, glycidyl ester type phenolic resins, aralkyl novolac phenolic resins, biphenyl aralkyl type phenolic resins, cresol novolac type phenolic resins, polyfunctional phenolic resins, naphthol resins, naphthol novolac resins, polyfunctional naphthol resins, anthracene type phenolic resins, naphthalene skeleton-modified novolac type phenolic resins, phenol aralkyl type phenolic resins, naphthol aralkyl type phenolic resins, dicyclopentadiene type phenolic resins, biphenyl type phenolic resins, alicyclic phenolic resins, polyol type phenolic resins, phosphorus-containing phenolic resins, and hydroxyl group-containing silicone resins. Among these, from the viewpoint of further improving the flame resistance of the resulting cured product, it is preferable to use at least one selected from the group consisting of biphenyl aralkyl phenolic resins, naphthol aralkyl phenolic resins, phosphorus-containing phenolic resins, and hydroxyl group-containing silicone resins.

[0061] The resin composition of the present embodiment preferably contains a phenolic compound within a range that does not impair the effects of the present invention. When the resin composition of the present embodiment contains a phenolic compound, the content thereof is preferably 0.1 parts by mass or more and 50 parts by mass or less per 100 parts by mass of the resin solid content in the resin composition. The resin composition of the present embodiment may contain only one type of phenol compound, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range. The resin composition of the present embodiment may be configured to be substantially free of phenolic compounds, meaning that the content of phenolic compounds is less than 0.1 parts by mass per 100 parts by mass of the resin solid content in the resin composition.

[0062] <<Oxetane resin>> The resin composition of the present embodiment may contain an oxetane resin. The oxetane resin is not particularly limited as long as it is a compound having one or more oxetanyl groups (preferably 2 to 12, more preferably 2 to 6, even more preferably 2 to 4, even more preferably 2 or 3, and still more preferably 2), and a wide range of compounds commonly used in the field of printed wiring boards can be used. Examples of oxetane resins include oxetane, alkyloxetane (e.g., 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3,3-dimethyloxetane, etc.), 3-methyl-3-methoxymethyloxetane, 3,3-di(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.).

[0063] The resin composition of this embodiment preferably contains an oxetane resin to a degree that does not impair the effects of the present invention. When the resin composition of this embodiment contains an oxetane resin, the content thereof is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 2 parts by mass or more, per 100 parts by mass of the resin solid content in the resin composition. When the oxetane resin content is 0.1 parts by mass or more, the metal foil peel strength and toughness tend to be improved. When the resin composition of this embodiment contains an oxetane resin, the upper limit of the oxetane resin content is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, and even more preferably 8 parts by mass or less, per 100 parts by mass of the resin solid content in the resin composition. When the oxetane resin content is 50 parts by mass or less, the electrical properties of the resulting cured product tend to be improved. The resin composition of the present embodiment may contain only one type of oxetane resin, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range. The resin composition of the present embodiment may be configured to be substantially free of oxetane resin, meaning that the content of oxetane resin is less than 0.1 parts by mass per 100 parts by mass of the resin solid content in the resin composition.

[0064] <<Benzoxazine compounds>> The resin composition of the present embodiment may contain a benzoxazine compound. The benzoxazine compound is not particularly limited as long as it has two or more (preferably 2 to 12, more preferably 2 to 6, even more preferably 2 to 4, still more preferably 2 or 3, and even more 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. Examples of benzoxazine compounds 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.).

[0065] 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 50 parts by mass or less per 100 parts by mass of the resin solid content in the resin composition. The resin composition of the present embodiment may contain only one type of benzoxazine compound, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range. The resin composition of the present embodiment may also be configured to be substantially free of benzoxazine compounds, meaning that the content of the benzoxazine compounds is less than 0.1 parts by mass per 100 parts by mass of the resin solid content in the resin composition.

[0066] <<Compounds having a polymerizable unsaturated group other than compound (B) containing two or more carbon-carbon unsaturated double bonds>> The resin composition of this 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 contained in the compound is 1 or more per molecule, preferably 2 to 12, more preferably 2 to 6, even more preferably 2 to 4, still more preferably 2 or 3, and even more preferably 2. The compound having a polymerizable unsaturated group other than the compound (B) containing 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. 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.), mono- or polyalcohol (meth)acrylates (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.

[0067] The resin composition of this embodiment preferably contains a compound having a polymerizable unsaturated group other than the compound (B) containing two or more carbon-carbon unsaturated double bonds, to the extent that the effects of the present invention are not impaired. When the resin composition of this embodiment contains a compound having a polymerizable unsaturated group other than the compound (B) containing two or more carbon-carbon unsaturated double bonds, the content thereof is preferably 0.1 parts by mass or more and preferably 50 parts by mass or less per 100 parts by mass of the resin solid content in the resin composition. The resin composition of 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. When two or more compounds are contained, the total amount is preferably within the above range. The resin composition of this embodiment may also be configured to be substantially free of compounds having polymerizable unsaturated groups other than the compound (B) containing two or more carbon-carbon unsaturated double bonds. "Substantially free" means that the content of compounds having polymerizable unsaturated groups other than the compound (B) containing two or more carbon-carbon unsaturated double bonds is less than 0.1 parts by mass per 100 parts by mass of the resin solid content in the resin composition.

[0068] <<Cyanate ester compounds>> The resin composition of the present embodiment may contain a cyanate ester compound. The cyanate ester compound is not particularly limited as long as it contains one or more (preferably 2 to 12, more preferably 2 to 6, even more preferably 2 to 4, still more preferably 2 or 3, and still more preferably 2) cyanate groups (cyanato groups) in one molecule, and a wide range of compounds commonly used in the field of printed wiring boards can be used. In addition, the cyanate ester compound is preferably a compound in which the cyanate group is directly bonded to an aromatic skeleton (aromatic ring). Examples of cyanate ester compounds include at least one selected from the group consisting of phenol novolac cyanate ester compounds, naphthol aralkyl cyanate ester compounds (naphthol aralkyl cyanates), naphthylene ether cyanate ester compounds, biphenyl aralkyl cyanate ester compounds, xylene resin cyanate ester compounds, trisphenolmethane cyanate ester compounds, adamantane skeleton cyanate ester compounds, bisphenol M cyanate ester compounds, bisphenol A cyanate ester compounds, and diallyl bisphenol A cyanate ester compounds. 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 cyanate ester compounds, naphthol aralkyl cyanate ester compounds, naphthylene ether cyanate ester compounds, xylene resin cyanate ester compounds, bisphenol M cyanate ester compounds, bisphenol A cyanate ester compounds, and diallyl bisphenol A cyanate ester compounds is preferred, and naphthol aralkyl cyanate ester compounds are more preferred. These cyanate ester compounds may be prepared by known methods, or commercially available products may be used. Note that cyanate ester compounds having a naphthol aralkyl skeleton, a naphthylene ether skeleton, a xylene skeleton, a trisphenolmethane skeleton, or an adamantane skeleton have a relatively large functional group equivalent weight and a small number of unreacted cyanate ester groups, so that cured products of resin compositions using these compounds tend to have even more excellent low water absorption. Furthermore, mainly due to the presence of an aromatic skeleton or an adamantane skeleton, plating adhesion tends to be even more improved.

[0069] The resin composition of this embodiment preferably contains a cyanate ester compound within a range that does not impair the effects of the present invention. When the resin composition of this embodiment contains a cyanate ester compound, the lower limit of the cyanate ester compound content is preferably 1 part by mass or more, more preferably 10 parts by mass or more, and even more preferably 20 parts by mass or more, per 100 parts by mass of the resin solids in the resin composition. When the cyanate ester compound content is 1 part by mass or more, preferably 10 parts by mass or more, and more preferably 20 parts by mass or more, the heat resistance, flame resistance, chemical resistance, low dielectric constant, low dielectric dissipation factor, and insulating properties of the resulting cured product tend to be improved. When the resin composition of this embodiment contains a cyanate ester compound, the upper limit of the cyanate ester compound content is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, even more preferably 70 parts by mass or less, even more preferably 60 parts by mass or less, and even more preferably 50 parts by mass or less, per 100 parts by mass of the resin solids in the resin composition. The resin composition of the present embodiment may contain only one type of cyanate ester compound, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range. The resin composition of the present embodiment may also be configured to be substantially free of cyanate ester compounds, which means that the content of the cyanate ester compounds is less than 0.1 parts by mass, preferably less than 0.01 parts by mass, and even less than 0.001 parts by mass, per 100 parts by mass of the resin solid content in the resin composition.

[0070] <<Elastomer>> The resin composition of the present embodiment may contain an elastomer. In this embodiment, the elastomer is not particularly limited and may be, 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. 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. From the viewpoint of even better 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.

[0071] In this embodiment, the elastomer has an SP value of 9 (cal / cm 3 ) 1 / 2 The SP value is called the solubility parameter, and is preferably 1 cm or less. 3 The square root of the heat of vaporization required to evaporate a liquid (cal / cm 3 ) 1 / 2 Generally, the smaller this value, the lower the polarity, and the closer these values ​​are, the higher the affinity between the two components. An elastomer with an SP value of 9 (cal / cm 3 ) 1 / 2 If the content is less than this, electrical properties more suitable for a resin composition used in a printed wiring board for high frequency applications can be obtained.

[0072] In this embodiment, if the elastomer has a weight-average molecular weight of 80,000 or more in terms of polystyrene measured by the GPC method and is solid at 25° C., it is preferable because crack resistance is further improved when used as a material for printed wiring boards (e.g., laminates, metal foil-clad laminates), etc. On the other hand, if the weight-average molecular weight of 40,000 or less in terms of polystyrene measured by the GPC method and is liquid at 25° C., warping is reduced when the film coated with the elastomer is laminated to a substrate, making it particularly suitable as a build-up material for printed wiring boards.

[0073] The resin composition of this embodiment preferably contains an elastomer to the extent that the effects of the present invention are not impaired. When the resin composition of this embodiment contains an elastomer, the content thereof is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 2 parts by mass or more, per 100 parts by mass of the resin solid content in the resin composition. When the resin composition of this embodiment contains an elastomer, the upper limit of the elastomer content is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, and even more preferably 8 parts by mass or less, per 100 parts by mass of the resin solid content in the resin composition. The resin composition in this embodiment may contain only one type of elastomer, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range. The resin composition of the present embodiment may also be configured to be substantially free of elastomer, meaning that the content of elastomer is less than 0.1 parts by mass per 100 parts by mass of the resin solid content in the resin composition.

[0074] <<Silane coupling agents>> The resin composition of the present embodiment may further contain a silane coupling agent, which tends to improve the dispersibility of the filler (D) described below and the adhesive strength between the resin component and the filler (D) and the substrate described below.

[0075] The silane coupling agent is not particularly limited as long as it is a silane coupling agent generally used for the surface treatment of inorganic materials, but examples thereof include vinylsilane compounds such as vinyltrimethoxysilane; styrylsilane compounds such as p-styryltrimethoxysilane; aminosilane compounds such as γ-aminopropyltriethoxysilane and N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane; epoxysilane compounds such as γ-glycidoxypropyltrimethoxysilane; acrylicsilane compounds such as γ-acryloxypropyltrimethoxysilane; cationic silane compounds such as N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride; and phenylsilane compounds. The silane coupling agents may be used alone or in combination of two or more.

[0076] When the resin composition of this embodiment contains a silane coupling agent, the lower limit of the content is preferably 0.005 parts by mass or more, more preferably 0.01 parts by mass or more, and even more preferably 0.1 parts by mass or more, per 100 parts by mass of the resin solid content in the resin composition. 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 even more preferably 2 parts by mass or less, per 100 parts by mass of the resin solid content in the resin composition. The silane coupling agent can be used alone or in combination of two or more. When two or more types are used, the total amount falls within the above range.

[0077] <<Activated ester compounds>> The resin composition of the present embodiment may contain an active ester compound. 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, even more preferably 2 to 4, still more preferably 2 or 3, and even more preferably 2) active ester groups in one molecule. The active ester compound may be a straight-chain, branched, or cyclic compound. Among these, from the viewpoint of further improving the heat resistance of the resulting cured product, an 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, an 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, an 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 per molecule is even more preferred, and an aromatic compound obtained by reacting a compound having at least two or more carboxylic acids per molecule with an aromatic compound having a phenolic hydroxyl group and having two or more active ester groups per molecule is particularly preferred. The carboxylic acid compound may be one or more 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 resulting cured product, one or more selected from the group consisting of succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid are preferred, and one or more selected from the group consisting of isophthalic acid and terephthalic acid are more preferred. The thiocarboxylic acid compound may be one or more selected from thioacetic acid and thiobenzoic acid. The phenol compound or naphthol compound may be at least one selected from the group consisting of hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalene, 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, dicyclopentadienyldiphenol, and phenol novolak. From the viewpoint of further improving the heat resistance and solvent solubility of the resulting cured product, bisphenol A, bisphenol F, bisphenol S, 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, dicyclopentadienyldiphenol, and phenol novolak. Preferred are 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, phloroglucinone, benzenetriol, dicyclopentadienyl diphenol, and phenol novolak, and more preferred are one or more selected from the group consisting of catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinone, benzenetriol, dicyclopentadienyl diphenol, and phenol novolak.More preferred is one or more selected from the group consisting of 6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyl diphenol, and phenol novolac, and particularly preferred is one or more selected from the group consisting of dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyl diphenol, and phenol novolac (preferably one or more selected from the group consisting of dicyclopentadienyl diphenol and phenol novolac, more preferably dicyclopentadienyl diphenol). The thiol compound may be one or more selected from the group consisting of benzenedithiol and triazinedithiol. In addition, from the viewpoint of further improving compatibility with the epoxy compound, the active ester compound is preferably a compound having at least two or more carboxylic acids in one molecule and containing an aliphatic chain, and from the viewpoint of further improving heat resistance, it is preferably a compound having an aromatic ring. More specific examples of the active ester compound include the active ester compounds described in JP-A-2004-277460.

[0078] The active ester compound may be a commercially available product or may be prepared by a known method. Commercially available products include compounds containing a dicyclopentadienyldiphenol structure (e.g., EXB9451, EXB9460, EXB9460S, HPC-8000-65T (all manufactured by DIC Corporation)), acetylated phenol novolac (e.g., DC808 (manufactured by Mitsubishi Chemical Corporation)), and benzoylated phenol novolac (e.g., YLH1026, YLH1030, YLH1048 (all manufactured by Mitsubishi Chemical Corporation)). EXB9460S is preferred from the viewpoints of further improving the storage stability of the varnish and the low coefficient of thermal expansion of the cured resin composition (cured product).

[0079] The active ester compound can be prepared by a known method, for example, by a condensation reaction between a carboxylic acid compound and a hydroxy compound. A specific example is a method of reacting (a) a carboxylic acid compound or its halide, (b) a hydroxy compound, and (c) an aromatic monohydroxy compound in a ratio of 0.05 to 0.75 moles of the phenolic hydroxyl group of (b) and 0.25 to 0.95 moles of (c) to 1 mole of the carboxyl group or acid halide group of (a).

[0080] 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 of the active ester compound is preferably 1 part by mass or more and 90 parts by mass or less per 100 parts by mass of the resin solid content in the resin composition. The resin composition of the present embodiment may contain only one type of active ester compound, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range. The resin composition of the present embodiment may also be configured to be substantially free of active ester compounds, meaning that the content of the active ester compounds is less than 1 part by mass per 100 parts by mass of the resin solid content in the resin composition.

[0081] <(D) Filler> The resin composition of the present embodiment preferably contains a filler (D). By blending the filler (D), the low dielectric constant, low dielectric loss tangent, flame resistance, and low thermal expansion of the resin composition can be further improved. Furthermore, the filler (D) used in this embodiment preferably has excellent dielectric properties. For example, the filler (D) used in this embodiment preferably has a dielectric constant (Dk) of 8.0 or less, more preferably 6.0 or less, measured according to the cavity resonance perturbation method. Furthermore, a practical lower limit for the dielectric constant is, for example, 2.0 or more. Furthermore, the filler (D) used in this embodiment preferably has a dielectric loss tangent (Df) of 0.05 or less, more preferably 0.01 or less, measured according to the cavity resonance perturbation method. Furthermore, a practical lower limit for the dielectric loss tangent is, for example, 0.0001 or more.

[0082] The filler (D) used in this embodiment is not particularly limited in type, and those generally used in the art can be suitably used.Specific examples include silicas such as natural silica, fused silica, synthetic silica, amorphous silica, aerosil, and hollow silica, white carbon, titanium white, zinc oxide, magnesium oxide, zirconium oxide, boron nitride, aggregated boron nitride, silicon nitride, aluminum nitride, barium sulfate, aluminum hydroxide, heat-treated aluminum hydroxide (aluminum hydroxide that has been heat-treated to remove some of the water of crystallization), boehmite, and metal hydrates such as magnesium hydroxide, molybdenum compounds such as molybdenum oxide and zinc molybdate, zinc borate, zinc stannate, alumina, clay, and the like. Examples of fillers include inorganic fillers such as kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, E-glass, A-glass, NE-glass, C-glass, L-glass, D-glass, S-glass, M-glass G20, short glass fibers (including fine glass powders such as E-glass, T-glass, D-glass, S-glass, and Q-glass), hollow glass, and spherical glass, as well as organic fillers such as styrene-type, butadiene-type, and acrylic-type rubber powders, core-shell-type rubber powders, silicone resin powders, silicone rubber powders, and silicone composite powders. Among these, one or more selected from the group consisting of silicas, aluminum hydroxide, boehmite, magnesium oxide and magnesium hydroxide are preferred. Use of these fillers improves the thermal expansion characteristics, dimensional stability, flame retardancy and other properties of the resin composition.

[0083] The content of the filler (D) in the resin composition of this embodiment can be appropriately set according to the desired properties and is not particularly limited, but is preferably 50 parts by mass or more, more preferably 75 parts by mass or more, relative to 100 parts by mass of the resin solid content in the resin composition. Furthermore, the content is preferably 1600 parts by mass or less, more preferably 1200 parts by mass or less, even more preferably 1000 parts by mass or less, still more preferably 750 parts by mass or less, even more preferably 500 parts by mass or less, still more preferably 300 parts by mass or less, 250 parts by mass or less, or 200 parts by mass or less, relative to 100 parts by mass of the resin solid content in the resin composition. In the resin composition of this embodiment, one preferred embodiment is one in which the content of the filler (D) is 30% by mass to 80% by mass of the components excluding the solvent. The resin composition in this embodiment may contain only one type of filler (D), or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

[0084] <Flame retardant> The resin composition of the present embodiment may contain a flame retardant. As the flame retardant, known ones can be used, for example, halogen-based flame retardants such as 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, and chlorinated paraffin, red phosphorus, tricresyl phosphate, triphenyl phosphate, and cresyl diphenyl phosphate. Examples of suitable flame retardants include phosphorus-based flame retardants such as phosphate, trixylenyl phosphate, trialkyl phosphate, dialkyl phosphate, tris(chloroethyl)phosphate, phosphazene, 1,3-phenylenebis(2,6-dixylenyl phosphate), and 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide; inorganic flame retardants such as aluminum hydroxide, magnesium hydroxide, partial boehmite, boehmite, zinc borate, and antimony trioxide; and silicone-based flame retardants such as silicone rubber and silicone resin. These flame retardants may be used alone or in combination of two or more. Among these, 1,3-phenylenebis(2,6-dixylenyl phosphate) is preferred because it does not impair low dielectric properties.

[0085] 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. The flame retardants can be used alone or in combination of two or more. When two or more types are used, the total amount falls within the above range.

[0086] <Dispersant> The resin composition of this embodiment may contain a dispersant. Dispersants commonly used in paints can be suitably used, and the type is not particularly limited. The dispersant is preferably a copolymer-based wetting dispersant, and specific examples thereof include DISPERBYK (registered trademark)-110, 111, 161, 180, 2009, 2152, 2155, BYK (registered trademark)-W996, W9010, W903, and W940, all manufactured by BYK Japan K.K.

[0087] When the resin composition of this embodiment contains a dispersant, the lower limit of the content thereof is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and may be 0.3 parts by mass or more, relative to 100 parts by mass of the resin solid content in the resin composition. The upper limit of the content of the dispersant is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 3 parts by mass or less, relative to 100 parts by mass of the resin solid content in the resin composition. The dispersant may be used alone or in combination of two or more. When two or more types are used, the total amount falls within the above range.

[0088] <Curing accelerator> The resin composition of the present embodiment may further contain a curing accelerator. The curing accelerator is not particularly limited, but examples thereof include imidazoles such as triphenylimidazole; organic peroxides such as benzoyl peroxide, lauroyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, and di-tert-butyl-diperphthalate; azo compounds such as azobisnitrile; N,N-dimethylbenzylamine, N,N-dimethylaniline, N,N-dimethyltoluidine, 2-N-ethylanilinoethanol, tri-n-butylamine, pyridine, quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, tetramethylbutanediamine, and N tertiary amines such as methylpiperidine; phenols such as phenol, xylenol, cresol, resorcinol, and catechol; organic metal salts such as lead naphthenate, lead stearate, zinc naphthenate, zinc octoate, manganese octoate, tin oleate, dibutyltin maleate, manganese naphthenate, cobalt naphthenate, and iron acetylacetonate; compounds obtained by dissolving these organic metal salts in hydroxyl group-containing compounds such as phenol and bisphenol; inorganic metal salts such as tin chloride, zinc chloride, and aluminum chloride; and organic tin compounds such as dioctyltin oxide, other alkyltins, and alkyltin oxides. Preferred curing accelerators are imidazoles and organic metal salts, and it is more preferred to use both imidazoles and organic metal salts in combination.

[0089] When the resin composition of this embodiment contains a curing accelerator, the lower limit of the content is preferably 0.005 parts by mass or more, more preferably 0.01 parts by mass or more, and even more preferably 0.1 parts by mass or more, per 100 parts by mass of the resin solid content in the resin composition. The upper limit of the content of the curing accelerator is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 2 parts by mass or less, per 100 parts by mass of the resin solid content in the resin composition. The curing accelerators can be used alone or in combination of two or more. When two or more types are used, the total amount falls within the above range.

[0090] <Solvent> The resin composition of this embodiment may contain a solvent, preferably an organic solvent. When a solvent is contained, the resin composition of this embodiment is in a form (solution or varnish) in which at least a portion, preferably all, of the various resin solid components described above are dissolved or compatible in the solvent. The solvent is not particularly limited as long as it is a polar or non-polar organic solvent that can dissolve or compatible in at least a portion, preferably all, of the various resin solid components described above. Examples of polar organic solvents include ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), cellosolves (e.g., propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.), esters (e.g., ethyl lactate, methyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate, methyl hydroxyisobutyrate, etc.), and amides (e.g., dimethoxyacetamide, dimethylformamide, etc.). Examples of non-polar organic solvents include aromatic hydrocarbons (e.g., toluene, xylene, etc.). The solvents can be used alone or in combination of two or more. When two or more solvents are used, the total amount falls within the above range.

[0091] <Other ingredients> In addition to the above components, the resin composition of this embodiment may contain various polymeric compounds such as thermoplastic resins and their oligomers, as well as various additives. Examples of additives include ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent brighteners, photosensitizers, dyes, pigments, thickeners, flow control agents, lubricants, antifoaming agents, leveling agents, gloss agents, and polymerization inhibitors. These additives may be used alone or in combination of two or more.

[0092] <Application> The resin composition of this embodiment is used as a cured product. Specifically, the resin composition of this embodiment can be suitably used as a low dielectric constant material and / or low dielectric loss tangent material, such as an insulating layer for a printed wiring board, a semiconductor package material, or other electronic material resin composition. The resin composition of this embodiment can be suitably used as a material for prepregs, metal foil-clad laminates using prepregs, resin sheets, and printed wiring boards. The resin composition of this embodiment is used as a layered material (including film and sheet forms) such as an insulating layer for a printed wiring board, a prepreg, or a resin sheet. When used as such a layered material, the thickness is preferably 5 μm or more, and more preferably 10 μm or more. The upper limit of the thickness is preferably 200 μm or less, and more preferably 180 μm or less. Note that the thickness of the layered material refers to the thickness including the glass cloth when, for example, the resin composition of this embodiment is impregnated into glass cloth or the like. The material formed from the resin composition of the present embodiment may be used for applications in which a pattern is formed by exposure and development, or for applications in which no exposure and development is required. It is particularly suitable for applications in which no exposure and development is required.

[0093] <<Prepreg>> The prepreg of this embodiment is formed from a substrate (prepreg substrate) and the resin composition of this embodiment. The prepreg of this embodiment can be obtained, for example, by applying the resin composition of this embodiment to the substrate (e.g., by impregnation and / or coating) and then semi-curing by heating (e.g., by drying at 120 to 220°C for 2 to 15 minutes). In this case, the amount of the resin composition attached to the substrate, i.e., 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, more preferably in the range of 20 to 80% by mass.

[0094] The substrate is not particularly limited as long as it is a substrate used in various printed wiring board materials. Examples of the substrate material 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 fabric, nonwoven fabric, roving, chopped strand mat, surfacing mat, etc. These substrates may be used alone or in combination of two or more. Among these substrates, woven fabrics that have been subjected to an ultra-opening treatment and a clogging treatment are preferred from the viewpoint of dimensional stability. From the viewpoint of strength and low water absorption, the substrate should have a thickness of 200 μm or less and a mass of 250 g / m. 2 The following glass woven fabrics are preferred, and from the viewpoint of moisture absorption and heat resistance, glass woven fabrics that have been surface-treated with a silane coupling agent such as epoxy silane treatment or amino silane treatment are preferred. From the viewpoint of electrical properties, low-dielectric glass cloths made of glass fibers that exhibit low dielectric constant and low dielectric loss tangent, such as L-glass, NE-glass, and Q-glass, are more preferred. An example of a substrate with a low dielectric constant is a substrate with a dielectric constant of 5.0 or less (preferably 3.0 to 4.9). An example of a substrate with a low dielectric loss tangent is a substrate with a dielectric loss tangent 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 method cavity resonator.

[0095] <<Metal foil clad laminate>> The metal foil-clad laminate of this embodiment includes at least one layer formed from the prepreg of this embodiment and a metal foil disposed on one or both sides of the layer formed from the prepreg. Examples of methods for producing the metal foil-clad laminate of this embodiment include a method in which at least one prepreg of this embodiment (preferably two or more prepregs) is disposed, and a metal foil is disposed on one or both sides of the prepreg, followed by lamination molding. More specifically, the metal foil-clad laminate of this embodiment can be produced by disposing a metal foil, such as copper or aluminum, on one or both sides of the prepreg, followed by lamination molding. The number of prepregs is preferably 1 to 10, more preferably 2 to 10, and even more preferably 2 to 9. The metal foil is not particularly limited as long as it is used as a material for printed wiring boards, and examples thereof include copper foils such as rolled copper foil and electrolytic copper foil. The thickness of the metal foil (preferably copper foil) is not particularly limited and may be approximately 1.5 to 70 μm. Examples of molding methods include methods commonly used for molding laminates and multilayer boards for printed wiring boards. More specifically, methods using a multistage press, multistage vacuum press, continuous molding machine, autoclave molding machine, etc., are used at a temperature of about 180 to 350°C, a heating time of about 100 to 300 minutes, and a surface pressure of 20 to 100 kg / cm. 2 Examples of suitable methods include lamination molding at approximately the same thickness. A multilayer board can also be produced by combining the prepreg of this embodiment with a separately prepared inner layer wiring board and laminating it together. A method for producing a multilayer board involves, for example, placing copper foil of approximately 35 μm on both sides of a single prepreg of this embodiment, laminating it using the above-described molding method, forming an inner layer circuit, and then blackening the circuit to form an inner layer circuit board. Then, the inner layer circuit board and the prepreg of this embodiment are alternately arranged one by one, and copper foil is placed on the outermost layer. The multilayer board can be produced by laminating and molding it under the above-described conditions, preferably under vacuum. The metal foil-clad laminate of this embodiment can be suitably used as a printed wiring board.

[0096] The metal foil-clad laminate of this embodiment preferably has a low dielectric constant (Dk) measured using laminate A from which the metal foil has been removed by etching. Specifically, the dielectric constant (Dk) of laminate A is preferably 3.5 or less, more preferably 3.4 or less, and even more preferably 3.3 or less. There is no particular restriction on the lower limit of the dielectric constant (Dk), but a value of 2.0 or more is practical, for example. Furthermore, the metal foil-clad laminate of this embodiment preferably has a low dielectric loss tangent (Df) measured using 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 even more preferably 0.0030 or less. There is no particular lower limit for the dielectric loss tangent (Df), but a value of 0.0001 or more is practical, for example. The dielectric constant (Dk) and the dielectric loss tangent (Df) are measured according to the method described in the examples below.

[0097] Furthermore, the metal foil-clad laminate of this embodiment preferably has a high glass transition temperature measured using laminate A from which the metal foil has been removed by etching. Specifically, the glass transition temperature of laminate A is preferably 180°C or higher, and more preferably 280°C or higher. A practical upper limit of the glass transition temperature is, for example, 400°C or lower. The glass transition temperature of the metal foil-clad laminate is measured as described in the Examples below.

[0098] The metal foil-clad laminate of this embodiment preferably has a water absorption of 0.8% by mass or less, more preferably 0.4% by mass or less, even more preferably 0.35% by mass or less, and even more preferably 0.20% by mass or less, after treatment at 121°C and 2 atmospheres for 1 hour in a pressure cooker tester in accordance with JIS C6485: 2008. The lower limit of the water absorption is, for example, 0% by mass. Furthermore, the metal foil-clad laminate of this embodiment preferably has a water absorption rate of 0.8% by mass or less, more preferably 0.4% by mass or less, even more preferably 0.35% by mass or less, and even more preferably 0.20% by mass or less, after treatment at 121°C and 2 atmospheres for 5 hours in a pressure cooker tester in accordance with JIS C6485: 2008. The lower limit of the water absorption rate is, for example, 0% by mass.

[0099] As described above, the resin composition for electronic materials obtained using the resin composition of the present embodiment (a resin composition including a combination of specific components) provides a cured product that has excellent properties such as heat resistance, low dielectric properties (low dielectric constant, low dielectric dissipation factor), low water absorption, chemical resistance, and desmear resistance.

[0100] <<Printed wiring boards>> The printed wiring board of this embodiment includes an insulating layer and a conductor layer disposed on the surface of the insulating layer, wherein the insulating layer includes at least one of a layer formed from the resin composition of this embodiment and a layer formed from the prepreg of this embodiment. Such a printed wiring board can be manufactured using conventional methods, and the manufacturing method is not particularly limited. An example of a method for manufacturing a printed wiring board is described below. First, a metal foil-clad laminate such as the metal foil-clad laminate described above is prepared. Next, the surface of the metal foil-clad laminate is etched to form an inner layer circuit, thereby producing an inner layer substrate. If necessary, the surface of the inner layer circuit of this inner layer substrate is subjected to a surface treatment to increase adhesive strength. Next, a required number of the prepregs described above are stacked on the surface of the inner layer circuit, and metal foil for an outer layer circuit is further laminated on the outside, followed by heating and pressurizing to form an integral mold. In this way, a multilayer laminate is manufactured, in which an insulating layer consisting of a substrate and a cured product of the resin composition is formed between the inner layer circuit and the metal foil for the outer layer circuit. Next, this multilayer laminate is subjected to drilling processing for through holes and via holes, and then a plated metal film is formed on the wall surface of the hole to provide electrical continuity between the inner layer circuit and the metal foil for the outer layer circuit.The metal foil for the outer layer circuit is then etched to form the outer layer circuit, thereby producing a printed wiring board.

[0101] The printed wiring board obtained in the above manufacturing example has an insulating layer and a conductor layer formed on the surface of this insulating layer, and the insulating layer contains the resin composition of this embodiment described above and / or its cured product. That is, the prepreg of this embodiment described above (for example, a prepreg formed from a base material and the resin composition of this embodiment impregnated or applied thereto), or the layer formed from the resin composition of the metal foil-clad laminate of this embodiment described above, serves as the insulating layer of this embodiment.

[0102] <<Resin sheet>> The resin sheet of this embodiment includes a support and a layer formed from the resin composition of this embodiment and disposed on the surface of the support. The resin sheet can be used as a build-up film or a dry film solder resist. There are no particular limitations on the method for producing the resin sheet, but an example of a method for obtaining a resin sheet includes applying (coating) a solution obtained by dissolving the resin composition of this embodiment in a solvent to a support and drying the applied solution.

[0103] Examples of the support used here include, but are not limited to, polyethylene film, polypropylene film, polycarbonate film, polyethylene terephthalate film, ethylene tetrafluoroethylene copolymer film, and release films obtained by applying a release agent to the surface of these films, organic film substrates such as polyimide film, conductive foils such as copper foil and aluminum foil, glass plates, SUS (Steel Use Stainless) plates, FRP (Fiber-Reinforced Plastics), and other plate-shaped materials.

[0104] Examples of application methods (coating methods) include methods in which a solution of the resin composition of this embodiment dissolved in a solvent is applied onto a support using a bar coater, die coater, doctor blade, baker applicator, or the like. Furthermore, after drying, a single-layer sheet can be obtained by peeling or etching the support from a resin sheet in which the support and the resin composition are laminated. It should be noted that a single-layer sheet can also be obtained without using a support by supplying a solution of the resin composition of this embodiment dissolved in a solvent into a mold having a sheet-shaped cavity and drying it to form it into a sheet.

[0105] In the production of the monolayer sheet or resin sheet of this embodiment, the drying conditions for removing the solvent are not particularly limited. However, because low temperatures tend to leave the solvent in the resin composition, and high temperatures accelerate curing of the resin composition, a temperature of 20°C to 200°C for 1 to 90 minutes is preferred. The monolayer sheet or resin sheet can be used in an uncured state after the solvent has been dried, or it can be used in a semi-cured (B-staged) state as needed. Furthermore, the thickness of the resin layer in the monolayer sheet or resin sheet of this embodiment can be adjusted by the concentration and coating thickness of the solution of the resin composition of this embodiment used for coating (coating). While not particularly limited, a thickness of 0.1 to 500 μm is preferred because a thicker coating thickness generally leads to more solvent remaining during drying. [Example]

[0106] The present invention will be explained in more detail below with reference to examples. The materials, amounts used, ratios, processing details, processing procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. If the measuring instruments used in the examples are difficult to obtain due to discontinuation or the like, measurements can be made using other instruments with equivalent performance.

[0107] <Synthesis Example 1: Synthesis of modified polyphenylene ether compound> <<Synthesis of Difunctional Phenylene Ether Oligomers>> A 12 L vertical reactor equipped with a stirrer, a thermometer, an air inlet tube, and a baffle plate was charged with 29.36 g (42.1 mmol) of CuBr, 1.81 g (10.5 mmol) of N,N'-di-t-butylethylenediamine, 67.77 g (671.0 mmol) of n-butyldimethylamine, and 2,600 g of toluene. The mixture was stirred at a reaction temperature of 40°C. 2,2',3,3',5,5'-hexamethyl-(1,1', A mixed solution of 129.32 g (0.48 mol) N,N'-di-t-butylethylenediamine (N,N'-biphenol), 878.4 g (7.2 mol) 2,6-dimethylphenol, 1.22 g (7.2 mmol) N,N'-di-t-butylethylenediamine, and 26.35 g (260.9 mmol) n-butyldimethylamine was added dropwise over 230 minutes while bubbling a mixed gas (nitrogen and air) adjusted to an oxygen concentration of 8% by volume at a flow rate of 5.2 L / min and stirring was continued. After the addition was completed, 1,500 g of water containing 48.06 g (126.4 mmol) of tetrasodium ethylenediaminetetraacetate was added to quench the reaction. The aqueous and organic layers were separated, and the organic layer was washed with 1 N aqueous hydrochloric acid and then with pure water. The resulting solution was concentrated to 50% by mass using an evaporator to obtain 1981 g of a toluene solution of a bifunctional phenylene ether oligomer (Resin "A"). The number average molecular weight of Resin "A" measured by GPC in terms of polystyrene was 1975, the weight average molecular weight measured by GPC in terms of polystyrene was 3514, and the hydroxyl equivalent was 990.

[0108] <<Synthesis of modified polyphenylene ether compounds>> A reactor equipped with a stirrer, thermometer, and reflux condenser was charged with 833.4 g of a toluene solution of resin "A," 76.7 g of vinylbenzyl chloride (Seimi Chemical Co., Ltd., "CMS-P"), 1,600 g of methylene chloride, 6.2 g of benzyldimethylamine, 199.5 g of purified water, and 83.6 g of a 30.5 wt% aqueous solution of NaOH. The mixture was stirred at 40°C. After 24 hours of stirring, the organic layer was washed with a 1N aqueous solution of hydrochloric acid and then purified water. The resulting solution was concentrated using an evaporator and added dropwise to methanol to solidify. The solid was recovered by filtration and vacuum dried to obtain 450.1 g of a modified polyphenylene ether compound. The modified polyphenylene ether compound had a number average molecular weight (Mw) of 2250 (based on polystyrene standards) by GPC, a weight average Mw of 3920 (based on polystyrene standards) by GPC, and a vinyl group equivalent of 1189 g / vinyl group.

[0109] Example 1 A varnish was obtained by dissolving and mixing 77 parts by weight of compound (A) represented by formula (M1) ("X9-450", manufactured by DIC Corporation, compound represented by formula (M1)), 20 parts by weight of the modified polyphenylene ether obtained in Synthesis Example 1, 3 parts by weight of a naphthalene skeleton-modified novolac-type epoxy resin ("HP-9900", manufactured by DIC Corporation), 150 parts by weight of fused silica ("SC2050-MNU", average particle size 0.5 μm (manufactured by Admatechs Co., Ltd.)), and 0.5 parts by weight of TPIZ (2,4,5-triphenylimidazole, catalyst) in methyl ethyl ketone. The amounts added above indicate the solid content. This varnish was further diluted with methyl ethyl ketone and impregnated into a 0.069 mm thick NE glass woven fabric (Tobo Co., Ltd., product number N3313), which was then dried by heating at 150°C for 5 minutes to obtain a prepreg with a resin composition amount (including filler) of 60% by mass, a glass cloth amount of 40% by mass, and a thickness of 100 μm. A metal foil-clad laminate was produced using the obtained prepreg, and various physical properties were measured.

[0110] Eight sheets of the obtained prepreg were stacked, and 12 μm thick electrolytic copper foil was placed on top and bottom, and a pressure of 30 kgf / cm was applied. 2Lamination molding was performed 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 Kinzoku Co., Ltd. The obtained metal foil-clad laminate or laminate A described below was used to evaluate formability (presence or absence of voids), glass transition temperature (Tg), dielectric constant (Dk), dielectric dissipation factor (Df), water absorption, chemical resistance, and desmear resistance. The evaluation results are shown in Table 1.

[0111] (Measurement and evaluation methods) (1) Formability (presence or absence of voids) The interior (insulating layer) of the metal foil-clad laminate was visually inspected, and those in which voids were observed were judged as "voids present," and those in which no voids were observed were judged as "voids absent." (2) Glass transition temperature (Tg) The glass transition temperature was measured using a dynamic viscoelasticity measuring device (DMA) in accordance with JIS-K7244-4:1999 (Plastics - Testing methods for dynamic mechanical properties - Part 4: Tensile vibration - Non-resonant method), starting at 30°C, ending at 400°C, heating at a rate of 5°C / min, measuring at a frequency of 1 Hz, and in a nitrogen atmosphere. The dynamic viscoelasticity of a laminate (hereinafter referred to as "Laminate A") in which the copper foil of the metal foil-clad laminate had been removed by etching was measured, and the maximum value of the loss tangent (tanδ) obtained was taken as the glass transition temperature. The dynamic viscoelasticity measuring device used was an EXSTAR6000 DMS6100 manufactured by Seiko Instruments Inc. The evaluation was as follows: A: 280℃ or higher B: 180℃ or higher but lower than 280℃ C: 100℃ or higher but lower than 180℃

[0112] (3) Dielectric constant (Dk) and dielectric loss tangent (Df): The dielectric constant (Dk) and dielectric loss tangent (Df) at 10 GHz were measured using the laminate A with a perturbation method cavity resonator. The perturbation method cavity resonator used was Agilent8722ES manufactured by Agilent Technologies. The evaluation was as follows: <dk> A: Below 3.3 B + 3.3 to 3.4 B - 3.4 to 3.5 C:3.5 Super <df> A: Below 0.0030 B + : Above 0.0030 and below 0.0035 B - : Above 0.0035 and below 0.0040 C: Above 0.0040

[0113] Also, after standing still 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. Evaluated as follows. <Dk (after water absorption)> A: Below 3.4 B: Above 3.4 and below 3.5 C: Above 3.5 <Df (after water absorption)> A: Below 0.0080 B: Above 0.0080 and below 0.0100 C: Above 0.0100

[0114] (4) Water absorption rate: Samples obtained by cutting the laminate A into 30 mm × 30 mm were used to measure the water absorption rate after being processed at 121°C and 2 atmospheres for 1 hour and 5 hours using a pressure cooker tester in accordance with JIS C6485:2008. In Table 1, "1h" corresponds to the water absorption rate after 1-hour processing, and "5h" corresponds to the water absorption rate after 5-hour processing. A pressure cooker tester of PC-3 type manufactured by Hirayama Seisakusho was used. Evaluated as follows. S + : Below 0.20 mass% S - : Above 0.20 mass% and below 0.35 mass% A: Above 0.35 mass% and below 0.4 mass% B: Above 0.4 mass% and below 0.8 mass% C: Above 0.8 mass% (5) Chemical resistance: Laminate A was cut into 50 mm x 50 mm samples and immersed in a 4N hydrochloric acid solution at 60°C for 1 hour or 2 hours. The mass loss rate (mass%) was calculated from the mass of laminate A before and after immersion. A smaller absolute value indicates better chemical resistance (acid resistance). Laminate A was also immersed in a 1N sodium hydroxide solution at 70°C for 1 hour or 2 hours. The mass loss rate (mass%) was calculated from the mass of laminate A before and after immersion and shown as an absolute value. A smaller absolute value indicates better chemical resistance (alkali resistance). The evaluation was as follows: S: 0.3% by mass or less A: More than 0.3 mass% and 1.0 mass% or less B: More than 1.0 mass% and 3.0 mass% or less C: More than 3.0% by mass

[0115] (6) Desmear resistance: The following immersion treatment was performed on laminate A. First, laminate A was immersed in a swelling liquid (Swelling Dip Securigant P, manufactured by Atotech Japan) at 80°C for 10 minutes. Next, the immersed laminate A was immersed in a roughening liquid (Concentrate Compact CP, manufactured by Atotech Japan) at 80°C for 5 minutes. Next, the immersed laminate A was immersed in a neutralizing liquid (Reduction Conditioner Securigant P500, manufactured by Atotech Japan) at 45°C for 10 minutes. The mass loss rate (% by mass) of laminate A after this series of immersion treatments was measured after one cycle, two cycles, and three cycles. In Table 1, "1 time" corresponds to the "mass loss rate (mass%) after one immersion treatment," "2 times" corresponds to the "mass loss rate (mass%) after two immersion treatments," and "3 times" corresponds to the "mass loss rate (mass%) after three immersion treatments." The values ​​are shown as absolute values. The evaluation was as follows: S: 0.50% by mass or less A: More than 0.50 mass% and 1.0 mass% or less B: More than 1.0 mass% and 3.0 mass% or less C: More than 3.0% by mass

[0116] Comparative Example 1 The same procedure was repeated in Example 1, except that the compound (A) represented by formula (M1) ("X9-450", manufactured by DIC Corporation) was replaced with the same amount of phenylmethane-type maleimide resin (manufactured by Daiwa Chemical Industry Co., Ltd., BMI-2300 (trade name)). The results are shown in Table 1.

[0117] Comparative Example 2 The same procedure was repeated in Example 1, except that the compound (A) represented by formula (M1) ("X9-450", manufactured by DIC Corporation) was replaced with the same amount of the compound shown in the structure below (BMI-70 (trade name), manufactured by K.I. Chemicals Co., Ltd.). The results are shown in Table 1. [ka] In the above, Me represents a methyl group and Et represents an ethyl group.

[0118] Example 2 The same procedures were carried out as in Example 1, except that the content of compound (A) represented by 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.

[0119] Comparative Example 3 The same procedure was repeated in Example 1, except that the compound (A) represented by formula (M1) ("X9-450", manufactured by DIC Corporation) was replaced with the same amount of a maleimide compound (MIR-3000 (trade name), manufactured by Nippon Kayaku Co., Ltd.). The results are shown in Table 1.

[0120] [Table 1] [Industrial Applicability]

[0121] As explained above, the resin composition of the present invention can be widely and effectively used in a variety of applications, such as electrical insulating materials, semiconductor plastic packages, sealing materials, adhesives, laminate materials, resists, build-up laminate materials, etc., in electrical and electronic materials, machine tool materials, and aviation materials, and can be particularly effectively used as a printed wiring board material that can accommodate the high integration and densification of recent information terminal devices, communication devices, etc. Furthermore, the metal foil-clad laminate of the present invention has particularly low water absorption, chemical resistance, desmear resistance, and heat resistance, and therefore has extremely high industrial practical applicability.< / df> < / dk>

Claims

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: Formula (M1) 【Chemistry 1】 (In formula (M1), R Ｍ１ , R Ｍ２ , R Ｍ３ , and R Ｍ４ R 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. R Ｍ７ and R Ｍ８ are each independently an alkyl group. mx is 1 or 2, and lx is 0 or 1. R Ｍ９ and R Ｍ１０ R 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; and nx represents an integer of 1 or more and 20 or less.

2. The resin composition according to claim 1, wherein the content of the compound (A) represented by formula (M1) is 1 to 90 parts by mass when the resin solid content in the resin composition is 100 parts by mass.

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

4. The resin composition according to any one of claims 1 to 3, further comprising one or more other resin components (C) selected from the group consisting of maleimide compounds other than the compound (A) represented by formula (M1), epoxy compounds, phenolic compounds, oxetane resins, benzoxazine compounds, compounds having a polymerizable unsaturated group other than the compound (B) containing two or more carbon-carbon unsaturated double bonds, and cyanate ester compounds.

5. The resin composition according to any one of claims 1 to 4, further comprising 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 per 100 parts by mass of resin solids.

7. The resin composition according to any one of claims 1 to 6, 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.

8. The resin composition according to any one of claims 1 to 6, wherein the compound (B) containing two or more carbon-carbon unsaturated double bonds includes a compound represented by formula (1): 【Chemistry 2】 (In formula (1), X represents an aromatic group, and —(Y—O)n ２ - 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; n １ represents an integer of 1 to 6, and n ２ represents an integer from 1 to 100, and n ３ represents an integer of 1 to 4.)

9. The resin composition according to any one of claims 1 to 8, which is for use in a printed wiring board.

10. A cured product of the resin composition according to any one of claims 1 to 9.

11. A prepreg formed from a substrate and the resin composition according to any one of claims 1 to 9.

12. A metal foil-clad laminate comprising at least one prepreg according to claim 11 and a metal foil disposed on one or both sides of the prepreg.

13. A resin sheet comprising a support and a layer formed from the resin composition according to any one of claims 1 to 9, disposed on a surface of the support.

14. A printed wiring board including an insulating layer and a conductor layer disposed on a surface of the insulating layer, A printed wiring board, wherein the insulating layer comprises at least one of a layer formed from the resin composition according to any one of claims 1 to 9 and a layer formed from the prepreg according to claim 11.

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