Maleimide resin compositions, prepregs, laminates, resin films, printed circuit boards, and semiconductor packages

Abstract

The present invention relates to a maleimide resin composition containing: (A) one or more substance selected from the group consisting of maleimide compounds having one or more N-substituted maleimide groups and derivatives thereof; and (B) a polymer having a hydrocarbon chain or a polyether chain in the main chain thereof, wherein component (A) contains (A1) a maleimide compound having one or more N-substituted maleimide groups and a molecular weight of less than 600 and (A2) a maleimide compound having one or more N-substituted maleimide groups and a molecular weight of 600 or more. The present invention also relates to a prepreg, a laminated board, a resin film, a printed wiring board, and a semiconductor package which are obtained by using the maleimide resin composition.

Description

[Technical Field]

[0001] This embodiment relates to maleimide resin compositions, prepregs, laminates, resin films, printed circuit boards, and semiconductor packages. [Background technology]

[0002] In mobile communication devices such as mobile phones, their base station equipment, network infrastructure equipment such as servers and routers, and electronic devices such as large computers, the speed and capacity of the signals used are increasing year by year. Accordingly, the substrate materials of printed circuit boards mounted on these electronic devices are required to have dielectric properties that can reduce the transmission loss of high-frequency signals [hereinafter sometimes referred to as "high-frequency properties"], that is, low relative permittivity and low dielectric loss tangent. In recent years, in addition to the electronic devices mentioned above, new systems handling high-frequency wireless signals are being put into practical use or are planned for practical use in ITS fields such as automobiles and transportation systems, as well as in the field of short-range indoor communications. Therefore, it is expected that the need for substrate materials with excellent high-frequency characteristics will increase for printed circuit boards used in these fields in the future.

[0003] Printed circuit boards (PCBs) are primarily required to possess heat resistance and low thermal expansion properties that can withstand the operating environment. Therefore, resins with excellent mechanical properties, such as maleimide compounds, have been used in PCBs. However, many of these resins with excellent mechanical properties contain polar groups, leaving room for improvement in high-frequency characteristics. Therefore, low-polarity polymers with excellent high-frequency properties, such as polyphenylene ether and polybutadiene, have been used in printed circuit boards where extremely low transmission loss is required. However, while these low-polarity polymers are effective in reducing dielectric loss tangent, they have problems with low heat resistance, a high coefficient of thermal expansion compared to metals, and inferior mechanical properties.

[0004] Methods for modifying low-polarity polymers are being investigated as ways to improve the compatibility of low-polarity polymers. Patent Document 1 discloses a thermosetting resin composition containing an inorganic filler, a polyimide compound, and a polybutadiene elastomer modified with an acid anhydride. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2018-012747 [Overview of the project] [Problems that the invention aims to solve]

[0006] In the thermosetting resin composition described in Patent Document 1, the compatibility between the polyimide compound and the polybutadiene elastomer is improved by modifying the polybutadiene elastomer with an acid anhydride. Incidentally, in recent years, substrate materials have been required for application in fifth-generation mobile communication system (5G) antennas that use radio waves in the frequency band above 6 GHz and millimeter-wave radars that use radio waves in the frequency band of 30 to 300 GHz. To achieve this, it is necessary to develop resin compositions that have improved dielectric properties above 10 GHz while also possessing good circuit embedding and moldability. A method of reducing the minimum melt viscosity of the resin composition is effective in obtaining good circuit embedding and moldability. However, with the technology described in Patent Document 1, it was difficult to reduce the minimum melt viscosity while maintaining good properties, and to achieve improvements in circuit embedding properties and moldability.

[0007] In view of the current situation, this embodiment aims to provide a maleimide resin composition that has excellent dielectric properties in the high frequency band of 10 GHz or higher while reducing the minimum melt viscosity, as well as a prepreg, laminate, resin film, multilayer printed circuit board, and semiconductor package using the maleimide resin composition. [Means for solving the problem]

[0008] As a result of further investigations to solve the above problems, the inventors have found that the following embodiments [1] to

[14] can solve the problems. [1](A)One or more selected from the group consisting of maleimide compounds having one or more N-substituted maleimide groups and derivatives thereof, (B) A polymer having hydrocarbon chains or polyether chains in its main chain, It contains, The aforementioned component (A) is, (A1) Maleimide compounds having one or more N-substituted maleimide groups with a molecular weight of less than 600, and (A2) A maleimide resin composition containing a maleimide compound having one or more N-substituted maleimide groups and having a molecular weight of 600 or more. [2] The maleimide resin composition according to [1] above, wherein the (A1) component is an aromatic bismaleimide compound. [3] The maleimide resin composition according to [1] or [2] above, wherein the (A2) component is a maleimide compound containing an alicyclic hydrocarbon group. [4] The maleimide resin composition according to [3] above, wherein the alicyclic hydrocarbon group is included as part of an indan ring. [5] The maleimide resin composition according to any one of [1] to [4] above, wherein component (B) is a polymer having a hydrocarbon chain in its main chain. [6] The maleimide resin composition according to any one of [1] to [5] above, wherein component (B) is a modified conjugated diene polymer (B1) obtained by modifying a conjugated diene polymer having vinyl groups in its side chains with (b2) a maleimide compound having two or more N-substituted maleimide groups. [7] The maleimide resin composition according to [6], wherein component (B1) has substituents on its side chain formed by the reaction of a vinyl group of component (b1) and an N-substituted maleimide group of component (b2). [8] The maleimide resin composition according to [6] or [7] above, wherein the (b1) component is polybutadiene having a 1,2-vinyl group. [9] The maleimide resin composition according to any one of [1] to [8] above, wherein the content ratio of component (A) to component (B) [(A) / (B)] is 0.3 to 3.0 by mass.

[10] A prepreg containing the maleimide resin composition described in any of [1] to [9] above.

[11] A laminate containing the prepreg described in

[10] above and a metal foil.

[12] A resin film containing the maleimide resin composition described in any of [1] to [9] above.

[13] A multilayer printed circuit board comprising one or more selected from the group consisting of the prepreg described in

[10] above, the laminate described in

[11] above, and the resin film described in

[12] above.

[14] A semiconductor package comprising semiconductor elements mounted on a multilayer printed circuit board as described in

[13] above. [Effects of the Invention]

[0009] According to this embodiment, it is possible to provide a maleimide resin composition that has excellent dielectric properties in the high frequency band of 10 GHz or higher while reducing the minimum melt viscosity, as well as a prepreg, laminate, resin film, multilayer printed circuit board, and semiconductor package using the maleimide resin composition. [Modes for carrying out the invention]

[0010] In this specification, numerical ranges indicated using "~" represent a range that includes the numbers before and after "~" as the minimum and maximum values, respectively. The lower and upper limits of the numerical ranges described herein may be arbitrarily combined with the lower or upper limits of other numerical ranges. In the numerical ranges described herein, the upper or lower limits of those ranges may be replaced with the values ​​shown in the examples. Unless otherwise specified, each component and material exemplified herein may be used alone or in combination of two or more. In this specification, the content of each component in a resin composition means the total amount of multiple substances present in the resin composition, unless otherwise specified, if multiple substances corresponding to each component are present in the resin composition. Embodiments that combine any combination of the information described herein are also included. The mechanism of action described herein is speculative and does not limit the mechanism by which the resin composition according to this embodiment exerts its effects.

[0011] In this specification, the term "compatibility" means that the resins are mixed together at the nanoscale, microscale, or visually, even if they are not necessarily miscible at the molecular level.

[0012] In this specification, "semi-cured product" is synonymous with a resin composition in the B-stage state as defined in JIS K 6800 (1985), and "cured product" is synonymous with a resin composition in the C-stage state as defined in JIS K 6800 (1985).

[0013] In this specification, the number-average molecular weight refers to the value measured in polystyrene equivalent by gel permeation chromatography (GPC), which can be specifically measured by the method described in the examples.

[0014] [Maleimide resin composition] The maleimide resin composition of this embodiment [hereinafter sometimes simply referred to as "resin composition"] is (A) One or more selected from the group consisting of maleimide compounds and derivatives thereof having one or more N-substituted maleimide groups [hereinafter, this may be referred to as "maleimide compound or derivative thereof (A)" or "component (A)"], (B) A polymer having hydrocarbon chains or polyether chains in its main chain [hereinafter sometimes referred to as "component (B)"] It contains, The aforementioned component (A) is, (A1) Maleimide compounds having a molecular weight of less than 600 and containing one or more N-substituted maleimide groups [hereinafter, these may be referred to as "maleimide compound (A1)" or "component (A1)"], and (A2) Contains a maleimide compound having one or more N-substituted maleimide groups with a molecular weight of 600 or more [hereinafter, this may be referred to as "maleimide compound (A2)" or "component (A2)"].

[0015] The reason why the maleimide resin composition of this embodiment can reduce the minimum melt viscosity while having excellent dielectric properties in the high frequency band of 10 GHz or higher is not clear, but it is presumed to be as follows. Maleimide compounds with high molecular weight have low crystallinity, resulting in excellent solvent solubility and compatibility with other resins, but their high viscosity leads to poor resin flowability. On the other hand, maleimide compounds with low molecular weight have high crystallinity, resulting in poor solvent solubility and compatibility with other resins, but their low viscosity leads to excellent resin flowability. In contrast, the maleimide resin composition of this embodiment reduces the minimum melt viscosity without impairing solvent solubility and compatibility with other resins by using a combination of maleimide compounds with high and low molecular weights. As a result, the maleimide resin composition of this embodiment has excellent circuit embedding properties and moldability. Furthermore, this resin composition not only exhibits excellent compatibility, but also superior heat resistance and low thermal expansion, and an unexpectedly reduced dielectric loss tangent. This is presumed to be due to the improved compatibility, which allowed the dielectric loss tangent reduction effect derived from component (B) and the excellent mechanical properties derived from the maleimide compound or its derivative (A) to be fully realized. The components of the resin composition of this embodiment will be described in detail below.

[0016] <Maleimide compound or its derivative (A)> Component (A) is one or more selected from the group consisting of maleimide compounds having one or more N-substituted maleimide groups and derivatives thereof, and contains (A1) a maleimide compound having one or more N-substituted maleimide groups with a molecular weight of less than 600, and (A2) a maleimide compound having one or more N-substituted maleimide groups with a molecular weight of 600 or more. Examples of the above-mentioned "derivatives of maleimide compounds having one or more N-substituted maleimide groups" include the addition reaction products of a maleimide compound having one or more N-substituted maleimide groups and a diamine compound (a2), as described later. (A) Component (A) may be used alone or in combination of two or more components.

[0017] Component (A) is preferably one or more compounds selected from the group consisting of (i) and (ii) below, from the viewpoint of compatibility with other resins, dielectric properties and adhesion to conductors. (i) A maleimide compound (a1) having one or more N-substituted maleimide groups [Hereinafter, this may be referred to as "maleimide compound (a1)" or "component (a1)".] (ii) An aminomaleimide compound having a structural unit derived from maleimide compound (a1) and a structural unit derived from diamine compound (a2) [hereinafter, this may be referred to as "aminomaleimide compound (AX)" or "(AX) component."]

[0018] (Maleimide compounds having one or more N-substituted maleimide groups (a1)) (a1) The component is not particularly limited as long as it is a maleimide compound having one or more N-substituted maleimide groups, for example, a maleimide compound containing one or more selected from the group consisting of a linear hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Among these, from the viewpoint of compatibility with other resins, dielectric properties, heat resistance, low thermal expansion, and mechanical properties, it is preferable to include a maleimide compound containing an alicyclic hydrocarbon group and a maleimide compound having a biphenyl aralkyl skeleton, and it is more preferable to include a maleimide compound containing an alicyclic hydrocarbon group. (a1) The component may be used alone or in combination of two or more components.

[0019] As the maleimide compound containing the above-mentioned alicyclic hydrocarbon group, maleimide compounds in which the alicyclic hydrocarbon group is included as part of a fused ring of an aromatic ring and an aliphatic ring are preferred. The condensed ring described above is preferably a condensed biringular structure, and more preferably an indan ring, from the viewpoint of compatibility with other resins, dielectric properties, adhesion to conductors, and ease of manufacture. In other words, it is preferable that the maleimide compound containing an alicyclic hydrocarbon group contains an indan ring, and that the alicyclic hydrocarbon group is included as part of the indan ring. In this specification, the term "indan ring" refers to a fused bicyclic structure consisting of an aromatic six-membered ring and a saturated aliphatic five-membered ring. At least one of the ring-forming carbon atoms that make up the indan ring has a bonding group for attaching to other groups constituting component (a1). The ring-forming carbon atoms having the bonding group and the other ring-forming carbon atoms may or may not have substituents other than the bonding group. In component (a1), the indan ring is preferably included as a divalent group represented by the following general formula (a1-1).

[0020] [ka] (In the formula, R a1 n1 is an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a hydroxyl group, or a mercapto group, and n1 is an integer from 0 to 3. a2 ~R a4 Each of these is an alkyl group having 1 to 10 carbon atoms. (* indicates a bonding site.)

[0021] In the above general formula (a1-1), R a1Examples of the alkyl group having 1 to 10 carbon atoms represented by include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, and the like. These alkyl groups may be either linear or branched. R a1 Examples of the alkyl group contained in the alkyloxy group having 1 to 10 carbon atoms and the alkylthio group having 1 to 10 carbon atoms represented by are the same as those of the alkyl group having 1 to 10 carbon atoms described above. R a1 Examples of the aryl group having 6 to 10 carbon atoms represented by include a phenyl group, a naphthyl group, and the like. R a1 Examples of the aryl group contained in the aryloxy group having 6 to 10 carbon atoms and the arylthio group having 6 to 10 carbon atoms represented by are the same as those of the aryl group having 6 to 10 carbon atoms described above. R a1 Examples of the cycloalkyl group having 3 to 10 carbon atoms represented by include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, and the like. When n1 in the general formula (a1-1) is an integer of 1 to 3, R a1 is preferably an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms from the viewpoints of solvent solubility and reactivity, and more preferably an alkyl group having 1 to 4 carbon atoms.

[0022] R a2 ~R a4 Examples of the alkyl group having 1 to 10 carbon atoms represented by include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, and the like. These alkyl groups may be either linear or branched. Among these, R a2 ~R a4 is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group. In the general formula (a1-1), n1 is an integer of 0 to 3. When n1 is 2 or 3, a plurality of Ra1 They may be the same or they may be different.

[0023] Among the above, the divalent group represented by the general formula (a1-1) is chosen because of its compatibility with other resins, dielectric properties, adhesion to conductors, and ease of manufacture, and because n1 is 0, R a2 ~R a4 A divalent group represented by the following formula (a1-1'), in which the first group is a methyl group, is preferred.

[0024] [ka] (In the formula, * represents a bonding site.)

[0025] As for the (a1) component containing the divalent group represented by the above general formula (a1-1), a component represented by the following general formula (a1-2) is preferred from the viewpoint of compatibility with other resins, dielectric properties, ease of manufacture, etc.

[0026] [ka] (In the formula, R a1 ~R a4 And n1 are the same as those in the general formula (a1-1) above. a5 Each of these is independently an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a nitro group, a hydroxyl group, or a mercapto group; each of these is independently an integer from 0 to 4; and each of these is a numerical value from 0.95 to 10.0.

[0027] In the above general formula (a1-2), multiple R a1 Multiple n1s, multiple R a5 Multiple n2s may be the same or different. Also, if n3 is greater than 1, multiple R a2 Multiple Rsa3 R with each other and with multiple Rs a4 Each of the members may be the same or different.

[0028] In the above general formula (a1-2), R a5 For an explanation of the C1-C10 alkyl groups, C1-C10 alkyloxy groups, C1-C10 alkylthio groups, C6-C10 aryl groups, C6-C10 aryloxy groups, C6-C10 arylthio groups, and C3-C10 cycloalkyl groups represented by R, see above. a1 This is the same explanation as for alkyl groups with 1 to 10 carbon atoms, alkyloxy groups with 1 to 10 carbon atoms, alkylthio groups with 1 to 10 carbon atoms, aryl groups with 6 to 10 carbon atoms, aryloxy groups with 6 to 10 carbon atoms, arylthio groups with 6 to 10 carbon atoms, and cycloalkyl groups with 3 to 10 carbon atoms. Among these, R a5 From the viewpoint of compatibility with other resins, dielectric properties, adhesion to conductors, and ease of manufacture, alkyl groups having 1 to 4 carbon atoms, cycloalkyl groups having 3 to 6 carbon atoms, and aryl groups having 6 to 10 carbon atoms are preferred, with alkyl groups having 1 to 3 carbon atoms being more preferred. In the above general formula (a1-2), n2 is an integer between 0 and 4, and is preferably an integer between 0 and 3, more preferably 0 or 2, from the viewpoint of compatibility with other resins, dielectric properties, adhesion to conductors, and ease of manufacture. Furthermore, when n2 is 1 or greater, the benzene ring and the N-substituted maleimide group have a twisted conformation, and solvent solubility tends to improve due to the suppression of intermolecular stacking. From a similar viewpoint, when n2 is 1 or greater, R a5 The substitution position is preferably the ortho position relative to the N-substituted maleimide group. In the above general formula (a1-2), n3 is preferably 0.98 to 8.0, more preferably 1.0 to 7.0, and even more preferably 1.1 to 6.0, from the viewpoint of compatibility with other resins, solvent solubility, melt viscosity, handling properties, and heat resistance.

[0029] The (a1) component represented by the above general formula (a1-2) is more preferably represented by the following general formula (a1-3) or the following general formula (a1-4).

[0030] [ka] (In the formula, R a1 ~R a5 n1 and n3 are the same as those in the general formula (a1-2) above.

[0031] TIFF0007865207000005.tif38166 (In the formula, R a1 ~R a4 n1 and n3 are the same as those in the general formula (a1-2) above.

[0032] Examples of component (a1) represented by the above general formula (a1-3) include the compound represented by the following general formula (a1-3-1), the compound represented by the following general formula (a1-3-2), and the compound represented by the following general formula (a1-3-3).

[0033] TIFF0007865207000006.tif118162 (In the formula, n3 is the same as the one in the general formula (a1-2) above.)

[0034] The compound represented by the above general formula (a1-4) is more preferably represented by the following general formula (a1-4-1) from the viewpoint of compatibility, solvent solubility, melt viscosity, handling properties, and heat resistance.

[0035] [ka] (In the formula, n3 is the same as the one in the general formula (a1-2) above.)

[0036] Preferred maleimide compounds having the biphenylaralkyl skeleton are those represented by the following general formulas (a1-5).

[0037] [ka] (n4 is an integer between 1 and 5.)

[0038] Examples of maleimide compounds other than maleimide compounds containing alicyclic hydrocarbon groups and maleimide compounds having a biphenylaralkyl skeleton (a1) [hereinafter sometimes referred to as "other maleimide compounds"] include maleimide compounds represented by the following general formula (a1-11).

[0039] [ka] (In the formula, X a1 These are divalent groups represented by the following general formulas (a1-12), (a1-13), (a1-14), or (a1-15). However, these groups do not include alicyclic hydrocarbon groups.

[0040] [ka] (In the formula, R a11 This refers to an aliphatic hydrocarbon group or halogen atom having 1 to 5 carbon atoms. p1 is an integer from 0 to 4. * represents a bonding site.

[0041] R a11 Examples of aliphatic hydrocarbon groups having 1 to 5 carbon atoms that can be represented by include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, and n-pentyl groups. Preferably, the aliphatic hydrocarbon group has 1 to 3 carbon atoms, more preferably an alkyl group has 1 to 3 carbon atoms, and even more preferably a methyl group. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. p1 is an integer from 0 to 4, preferably an integer from 0 to 2, more preferably 0 or 1, and even more preferably 0, from the viewpoint of availability. If p1 is an integer of 2 or more, multiple R a11 The same or different items may be the same or different.

[0042] [ka] (In the formula, R a12 and R a13 Each of these is independently an aliphatic hydrocarbon group or halogen atom having 1 to 5 carbon atoms. a2 is an alkylene group with 1 to 5 carbon atoms, an alkylidene group with 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, a single bond, or a divalent group represented by the following general formula (a1-13-1). p2 and p3 are each independently integers from 0 to 4. * represents a bonding site.

[0043] R a12 and R a13 The aliphatic hydrocarbon group with 1 to 5 carbon atoms and halogen atoms represented by are: a11 The same explanation applies as in the previous case. The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably an ethyl group.

[0044] X a2 Examples of alkylene groups having 1 to 5 carbon atoms include methylene groups, 1,2-dimethylene groups, 1,3-trimethylene groups, 1,4-tetramethylene groups, and 1,5-pentamethylene groups. From the viewpoint of compatibility with other resins, adhesion to conductors, heat resistance, low thermal expansion, and mechanical properties, alkylene groups having 1 to 3 carbon atoms are preferred, alkylene groups having 1 or 2 carbon atoms are more preferred, and methylene groups are even more preferred.

[0045] X a2Examples of alkylidene groups having 2 to 5 carbon atoms include ethylidene, propyridene, isopropylidene, butyridene, isobutylidene, pentyridene, and isopentylidene. Among these, isopropylidene is preferred from the viewpoint of compatibility with other resins, adhesion to conductors, heat resistance, low thermal expansion, and mechanical properties.

[0046] p2 and p3 are each an integer between 0 and 4, and from the viewpoint of availability, both are preferably integers between 0 and 3, more preferably integers between 0 and 2, and even more preferably 0 or 2. If p2 or p3 is an integer of 2 or more, multiple R a12 Mutual or R a13 They may be the same or they may be different.

[0047] Note X a2 The divalent group represented by the general formula (a1-13-1) is as follows:

[0048] [ka] (In the formula, R a14 and R a15 Each of these is independently an aliphatic hydrocarbon group or halogen atom having 1 to 5 carbon atoms. a3 The group is an alkylene group with 1 to 5 carbon atoms, an alkylidene group with 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, or a single bond. p4 and p5 are each independently integers from 0 to 4. * indicates a bonding site.

[0049] R a14 and R a15 The aliphatic hydrocarbon group with 1 to 5 carbon atoms represented by R is an aliphatic hydrocarbon group with 1 to 5 carbon atoms, and the halogen atom is R. a11 It is explained in the same way as in the case of this example. X a3 The alkylene group with 1 to 5 carbon atoms and the alkylidene group with 2 to 5 carbon atoms represented by are: a2 Examples include alkylene groups with 1 to 5 carbon atoms and alkylidene groups with 2 to 5 carbon atoms, which are the same as those represented by [the symbol]. X a3 Among the above options, alkylidene groups having 2 to 5 carbon atoms are preferred, alkylidene groups having 2 to 4 carbon atoms are more preferred, and isopropylidene groups are even more preferred. p4 and p5 are each an integer between 0 and 4, and from the viewpoint of availability, both are preferably integers between 0 and 2, more preferably 0 or 1, and even more preferably 0. If p4 or p5 is an integer of 2 or more, multiple R a14 Mutual or R a15 They may be the same or they may be different.

[0050] X a2 Among the above options, alkylene groups having 1 to 5 carbon atoms, alkylidene groups having 2 to 5 carbon atoms, and divalent groups represented by the above general formula (a1-13-1) are preferred.

[0051] [ka] (In the formula, p6 is an integer between 0 and 10. * represents a bonding site.)

[0052] From the viewpoint of availability, p6 is preferably an integer between 0 and 5, more preferably an integer between 0 and 4, and even more preferably an integer between 0 and 3.

[0053] [ka] (In the formula, R a16 and R a17 Each of these is independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. p7 is an integer from 1 to 8. * represents a bonding site.

[0054] R a16 and R a17 As an example of an aliphatic hydrocarbon group with 1 to 5 carbon atoms represented by R, a11 It is explained in the same way as in the case of this example. p7 is an integer between 1 and 8, preferably between 1 and 5, more preferably between 1 and 3, and even more preferably 1. If p7 is an integer greater than or equal to 2, then multiple R a16 Mutual or R a17 They may be the same or they may be different.

[0055] Other specific examples of maleimide compounds include aromatic bismaleimide compounds having two N-substituted maleimide groups bonded to an aromatic ring within the molecule, such as 4,4'-diphenylmethanebismaleimide, bis(4-maleimidophenyl) ether, bis(4-maleimidophenyl) sulfone, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, m-phenylenebismaleimide, and 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane; aromatic polymaleimide compounds having three or more N-substituted maleimide groups bonded to an aromatic ring within the molecule, such as polyphenylmethanemaleimide; and aliphatic maleimide compounds having N-substituted maleimide groups bonded to an aliphatic hydrocarbon group within the molecule, such as 1,6-bismaleimide-(2,2,4-trimethyl)hexane and pyrophosphate binder-type long-chain alkylbismaleimide.

[0056] (Aminomaleimide compound (AX)) Component (AX) is an aminomaleimide compound having structural units derived from maleimide compound (a1) and diamine compound (a2). The (AX) component may be used alone or in combination of two or more types.

[0057] [Structural unit derived from maleimide compound (a1)] Examples of structural units derived from component (a1) include structural units formed when at least one N-substituted maleimide group of component (a1) undergoes a Michael addition reaction with an amino group of the diamine compound (a2). The structural units derived from component (a1) contained in component (AX) may be one type alone or two or more types.

[0058] The content of structural units derived from component (a1) in the aminomaleimide compound (AX) is not particularly limited, but is preferably 5 to 95% by mass, more preferably 30 to 93% by mass, even more preferably 60 to 90% by mass, and particularly preferably 75 to 90% by mass. When the content of structural units derived from component (a1) is within the above range, dielectric properties and film handling properties tend to be better.

[0059] [Structural unit derived from diamine compound (a2)] Examples of structural units derived from component (a2) include structural units formed when one or both of the two amino groups of component (a2) undergo a Michael addition reaction with the N-substituted maleimide group of maleimide compound (a1). The structural units derived from component (a2) contained in component (AX) may be one type alone or two or more types.

[0060] (a2) The amino group of component is preferably a primary amino group. Examples of structural units derived from diamine compounds having two primary amino groups include the group represented by the following general formula (a2-1) and the group represented by the following general formula (a2-2).

[0061] [ka] (In the formula, X a11 (where * indicates a divalent organic group, and * indicates a bond position to other structures.)

[0062] X in the above general formulas (a2-1) and (a2-2) a11 This is a divalent organic group, and corresponds to the divalent group obtained by removing two amino groups from component (a2).

[0063] X in the above general formula (a2-1) and the above general formula (a2-2) a11 It is preferable that the group is a divalent group represented by the following general formula (a2-3).

[0064] [ka] (In the formula, R a21 and R a22 Each of these is independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, or a halogen atom. a12 This refers to an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, a fluorenylene group, a single bond, or a divalent group represented by the following general formula (a2-3-1) or (a2-3-2). p11 and p12 are each independently integers from 0 to 4. * represents a bonding site.

[0065] [ka] (In the formula, R a23 and R a24 Each of these is independently an aliphatic hydrocarbon group or halogen atom having 1 to 5 carbon atoms. a13 The group is an alkylene group with 1 to 5 carbon atoms, an alkylidene group with 2 to 5 carbon atoms, an m-phenylenediisopropylidene group, a p-phenylenediisopropylidene group, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, or a single bond. p13 and p14 are each independently integers from 0 to 4. * indicates a bonding site.

[0066] [ka] (In the formula, R a25 X is an aliphatic hydrocarbon group or halogen atom having 1 to 5 carbon atoms. a14 and X a15is independently an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group or a single bond. p15 is an integer of 0 to 4. * represents a bonding site.)

[0067] In the general formula (a2-3), the general formula (a2-3-1) and R in the general formula (a2-3-2) a21 , R a22 , R a23 , R a24 and R a25 Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms or the halogen atom represented by are the same as those of R a11 in the general formula (a1-12). As the aliphatic hydrocarbon group, an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group and an ethyl group are even more preferable. X a12 in the general formula (a2-3), X a13 in the general formula (a2-3-1), and X a14 and X a15 in the general formula (a2-3-2) are described in the same manner as in the case of X a2 in the general formula (a1-13).

[0068] In the general formula (a2-3), p11 and p12 are each independently an integer of 0 to 4, and from the viewpoint of availability, both are preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and even more preferably 0 or 2. When p11 and p12 are integers of 2 or more, a plurality of R a21 each other or R a22 each other may be the same or different. In the general formula (a2-3-1), p13 and p14 are each independently an integer of 0 to 4, and from the viewpoint of availability, both are preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0. When p13 and p14 are integers of 2 or more, a plurality of R a23 each other or R a24They may be the same or they may be different. In the above general formula (a2-3-2), p15 is an integer between 0 and 4, and from the viewpoint of availability, it is preferably an integer between 0 and 2, more preferably 0 or 1, and even more preferably 0. If p15 is an integer greater than or equal to 2, then multiple R a25 They may be the same or they may be different.

[0069] The content of structural units derived from component (a2) in the aminomaleimide compound (AX) is not particularly limited, but is preferably 5 to 95% by mass, more preferably 7 to 70% by mass, even more preferably 10 to 40% by mass, and particularly preferably 10 to 25% by mass. When the content of structural units derived from component (a2) is within the above range, dielectric properties, heat resistance, flame retardancy, and glass transition temperature tend to be better.

[0070] In the aminomaleimide compound (AX), the equivalence ratio (Ta2) of the total equivalent weight (Ta2) of groups derived from the -NH2 group of the diamine compound (a2) (including -NH2) to the total equivalent weight (Ta1) of groups derived from the N-substituted maleimide group of the maleimide compound (a1) (including N-substituted maleimide groups) is not particularly limited, but is preferably 0.05 to 10, more preferably 0.5 to 7, and even more preferably 1 to 5. When the equivalence ratio (Ta2 / Ta1) is within the above range, dielectric properties, heat resistance, flame retardancy, and glass transition temperature tend to be better.

[0071] The number-average molecular weight of the aminomaleimide compound (AX) is not particularly limited, but is preferably 400 to 10,000, more preferably 500 to 5,000, even more preferably 600 to 2,000, and most preferably 700 to 1,500.

[0072] (a2)Specific examples of components include 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ketone, 4,4'-diaminobiphenyl, 3,3'-dimethyl Tyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane, 2,2-bis(4-aminophenyl)propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 1,3-bi 3-(aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 1,3-bis[1-[4-(4-aminophenoxy)phenyl]-1-methylethyl]benzene, 1,4-bis[1-[4-(4-aminophenoxy)phenyl]-1-methylethyl]benzene, 4,4'-[1,3 Examples include -phenylenebis(1-methylethylidene)bisaniline, 4,4'-[1,4-phenylenebis(1-methylethylidene)]bisaniline, 3,3'-[1,3-phenylenebis(1-methylethylidene)]bisaniline, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, and 9,9-bis(4-aminophenyl)fluorene.

[0073] Among these, as component (a2), 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4,4'-[1,3-phenylenebis(1-methylethylidene)]bisaniline, and 4,4'-[1,4-phenylenebis(1-methylethylidene)]bisaniline are preferred from the viewpoint of excellent solubility in organic solvents, reactivity with maleimide compound (a1), and heat resistance. Furthermore, as component (a2), 3,3'-dimethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane is preferred from the viewpoint of excellent dielectric properties and low water absorption. Furthermore, from the viewpoint of excellent mechanical properties such as high adhesion to conductors, elongation, and tensile strength, 2,2-bis[4-(4-aminophenoxy)phenyl]propane is preferred for component (a2). In addition, from the viewpoint of excellent solubility in organic solvents, reactivity during synthesis, heat resistance, and high adhesion to conductors, as well as excellent dielectric properties and low hygroscopicity, 4,4'-[1,3-phenylenebis(1-methylethylidene)]bisaniline and 4,4'-[1,4-phenylenebis(1-methylethylidene)]bisaniline are preferred for component (a2).

[0074] (Method for producing aminomaleimide compounds (AX)) Component (AX) can be produced, for example, by reacting a maleimide compound (a1) and a diamine compound (a2) in an organic solvent. By reacting maleimide compound (a1) with diamine compound (a2), an aminomaleimide compound (AX) is obtained through a Michael addition reaction between maleimide compound (a1) and diamine compound (a2). When reacting the maleimide compound (a1) with the diamine compound (a2), a reaction catalyst may be used as needed. Examples of reaction catalysts include acidic catalysts such as p-toluenesulfonic acid; amines such as triethylamine, pyridine, and tributylamine; imidazoles such as methylimidazole and phenylimidazole; and phosphorus-based catalysts such as triphenylphosphine. The reaction catalyst may be used alone or in combination of two or more types. Furthermore, the amount of reaction catalyst added is not particularly limited, but for example, it is 0.01 to 5 parts by mass per 100 parts by mass of the total amount of maleimide compound (a1) and diamine compound (a2).

[0075] The reaction temperature for the above reaction is preferably 50 to 160°C, from the viewpoint of workability such as reaction rate and suppression of gelation during the reaction. Similarly, the reaction time for the above reaction is preferably 1 to 10 hours. Furthermore, in this step, the solid content concentration of the reaction raw materials and the viscosity of the solution may be adjusted by adding or concentrating an organic solvent. The solid content concentration of the reaction raw materials is not particularly limited, but is preferably 10 to 90% by mass, more preferably 15 to 85% by mass, and even more preferably 20 to 80% by mass. When the solid content concentration of the reaction raw materials is above the lower limit, a good reaction rate is obtained and productivity tends to be better. Also, when the solid content concentration of the reaction raw materials is below the upper limit, better solubility is obtained, stirring efficiency is improved, and gelation tends to be further suppressed.

[0076] (Component A1 and component A2) Component (A) contains, as described above, (A1) a maleimide compound having one or more N-substituted maleimide groups with a molecular weight of less than 600, and (A2) a maleimide compound having one or more N-substituted maleimide groups with a molecular weight of 600 or more. In this embodiment, the "molecular weight" of components (A1) and (A2) refers to the molecular weight that can be calculated from the structural formula if the compound is not a polymer and the structural formula of the compound can be identified, and the number-average molecular weight if the compound is a polymer.

[0077] [Component (A1)] Component (A1) can be, for example, one of the maleimide compounds (a1) listed above that has a molecular weight of less than 600. Among these, aromatic bismaleimide compounds with a molecular weight of less than 600 are preferred, and aromatic bismaleimide compounds represented by the general formula (a1-11) above that have a molecular weight of less than 600 are more preferred. In this specification, an aromatic bismaleimide compound means a compound having two N-substituted maleimide groups directly bonded to an aromatic ring. (A1) Component (A1) may be used alone or in combination of two or more components.

[0078] (A1)Specific examples of component include 4,4'-diphenylmethanebismaleimide, bis(4-maleimidophenyl) ether, bis(4-maleimidophenyl) sulfone, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, m-phenylenebismaleimide, and 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane. Among these, 4,4'-diphenylmethanebismaleimide, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, and 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide are preferred. The molecular weight of component (A1) is not particularly limited as long as it is in the range of less than 600, and can be determined according to the desired performance. For example, from the viewpoint of further improving the flowability of the resin and further reducing the minimum melt viscosity, it may be less than 550, less than 500, or less than 450. Also, the lower limit of the molecular weight of component (A1) may be 200 or more, or 300 or more.

[0079] [(A2) component] (A2) Examples of components include those listed as maleimide compounds (a1) above, with a molecular weight of 600 or more. Among these, maleimide compounds containing the alicyclic hydrocarbon group described above are preferred, maleimide compounds containing an indan ring are more preferred, maleimide compounds represented by the above general formula (a1-2) are even more preferred, and maleimide compounds represented by the above general formula (a1-3) or the above general formula (a1-4) are particularly preferred. (A2) The component may be used alone or in combination of two or more components.

[0080] The molecular weight of component (A2) is not particularly limited as long as it is in the range of 600 or more, and can be determined according to the desired performance. For example, from the viewpoint of further improving solvent solubility and compatibility with other resins, it may be 650 or more, 700 or more, or 750 or more. Furthermore, the upper limit of the molecular weight of component (A2) may be 10,000 or less, or 7,000 or less.

[0081] [Ratio of content of component (A1) and component (A2)] In the resin composition of this embodiment, the content ratio of component (A1) to component (A2) [(A1) / (A2)] is not particularly limited, but from the viewpoint of compatibility with other resins, dielectric properties, low thermal expansion, and heat resistance, it is preferably 5 / 95 to 50 / 50 by mass, more preferably 10 / 90 to 45 / 55, even more preferably 15 / 85 to 40 / 60, and particularly preferably 20 / 80 to 35 / 65. When the above content ratio [(A1) / (A2)] is 5 / 95 or higher, moldability and processability tend to be better, and when it is 50 / 50 or lower, dielectric properties, mechanical properties, and flame retardancy tend to be better. The total content of components (A1) and (A2) in component (A) is not particularly limited, but from the viewpoint of dielectric properties, mechanical properties, flame retardancy, formability and processability, it is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more, and may be 100% by mass.

[0082] <(B) Polymers having hydrocarbon chains or polyether chains in the main chain> Component (B) is a polymer having hydrocarbon chains or polyether chains in its main chain, and is a component that contributes to improving dielectric properties. In this embodiment, "main chain" refers to the relatively longest bonding chain in the polymer molecule, and "side chain" refers to an atomic group branching off from the main chain. Furthermore, in this embodiment, "hydrocarbon chain" refers to a structure in which carbon atoms bonded to hydrogen atoms are linked together in a chain. Furthermore, in this embodiment, "polyether chain" refers to a structure in which units containing polyether bonds are linked together in a chain. (B) Component may be used alone or in combination of two or more types.

[0083] Examples of polymers having hydrocarbon chains in the main chain include conjugated diene polymers, styrene elastomers, and modified versions thereof. Examples of polymers having polyether chains in the main chain include polyphenylene ethers and modified versions of polyphenylene ethers. Among these, polymers having hydrocarbon chains in the main chain are preferred from the viewpoint of compatibility with other resins, dielectric properties, and heat resistance, and modified conjugated diene polymers and styrene elastomers are more preferred. From a similar viewpoint, as a modified conjugated diene polymer, a modified conjugated diene polymer (B1) obtained by modifying (b1) a conjugated diene polymer having vinyl groups in the side chain with (b2) a maleimide compound having two or more N-substituted maleimide groups is preferred. Hereinafter, the modified conjugated diene polymer (B1) will be referred to as "component (B1)," and the styrene elastomer may be referred to as "styrene elastomer (B2)" or "component (B2)."

[0084] (Modified conjugated diene polymer (B1)) Component (B1) is obtained by modifying (b1) a conjugated diene polymer having vinyl groups in its side chains [hereinafter, it may be referred to as "conjugated diene polymer (b1)" or "component (b1)"] with (b2) a maleimide compound having two or more N-substituted maleimide groups [hereinafter, it may be referred to as "maleimide compound (b2)" or "component (b2)"]. By using component (B1) as component (B), the compatibility, dielectric properties, heat resistance, and low thermal expansion of the cured resin composition tend to be further improved. This is presumed to be because the N-substituted maleimide groups introduced into the conjugated diene polymer react well with the maleimide compound or its derivative (A), further improving compatibility with the maleimide compound or its derivative (A) and improving the overall curability of the resin composition. (B1) Component may be used alone or in combination of two or more types.

[0085] [(b1) Conjugated diene polymer having vinyl groups in its side chains] (b1) The component is not particularly limited as long as it is a conjugated diene polymer having vinyl groups in its side chains. (b1) The component may be used alone or in combination of two or more components.

[0086] (b1) Component is preferably a conjugated diene polymer having multiple vinyl groups in its side chains. The number of vinyl groups in one molecule of component (b1) is not particularly limited, but from the viewpoint of dielectric properties and heat resistance, it is preferably 3 or more, more preferably 5 or more, and even more preferably 10 or more.

[0087] In this specification, "conjugated diene polymer" means a polymer of a conjugated diene compound. Examples of conjugated diene compounds include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, and 1,3-hexadiene. The conjugated diene polymer may be a polymer of one conjugated diene compound, or it may be a polymer of two or more conjugated diene compounds. Furthermore, the conjugated diene polymer may be obtained by copolymerizing one or more conjugated diene compounds with one or more monomers other than conjugated diene compounds. In this case, the polymerization method is not particularly limited and may be random polymerization, block polymerization, or graft polymerization.

[0088] (b1) Specific examples of component include polybutadiene having 1,2-vinyl groups, butadiene-styrene copolymer having 1,2-vinyl groups, and polyisoprene having 1,2-vinyl groups. Among these, polybutadiene having 1,2-vinyl groups and butadiene-styrene copolymer having 1,2-vinyl groups are preferred from the viewpoint of dielectric properties and heat resistance, and polybutadiene having 1,2-vinyl groups is more preferred. Furthermore, as polybutadiene having 1,2-vinyl groups, butadiene homopolymer having 1,2-vinyl groups is preferred. (b1) The 1,2-vinyl group derived from butadiene in component (b1) is the vinyl group contained in the butadiene-derived structural unit represented by the following formula (b1-1).

[0089] [ka]

[0090] (b1) When component (b1) is polybutadiene having 1,2-vinyl groups, the content of structural units having 1,2-vinyl groups relative to the total structural units derived from butadiene constituting the polybutadiene [hereinafter sometimes referred to as "vinyl group content"] is not particularly limited, but from the viewpoint of compatibility with other resins, dielectric properties, low thermal expansion and heat resistance, it is preferably 50 mol% or more, more preferably 60 mol% or more, even more preferably 70 mol% or more, particularly preferably 80 mol% or more, and most preferably 85 mol% or more. Furthermore, there is no particular upper limit to the vinyl group content, and it may be 100 mol% or less, 97 mol% or less, or 95 mol% or less. As structural units having 1,2-vinyl groups, structural units derived from butadiene represented by the above formula (b1-1) are preferred. From a similar viewpoint, the polybutadiene having a 1,2-vinyl group is preferably a 1,2-polybutadiene homopolymer.

[0091] (b1) The number-average molecular weight of component is not particularly limited, but from the viewpoint of compatibility with other resins, dielectric properties, low thermal expansion, and heat resistance, it is preferably 400 to 4,000, more preferably 500 to 3,000, even more preferably 600 to 2,000, and especially preferably 700 to 1,500.

[0092] ((b2) Maleimide compounds having two or more N-substituted maleimide groups) (b2) Component can be any maleimide compound having two or more N-substituted maleimide groups, and any of the maleimide compounds listed as (A) above can be used. (b2) The component may be used alone or in combination of two or more components.

[0093] Among these, as component (b2), the bismaleimide compound represented by (a1-11) above is preferred from the viewpoint of solubility in organic solvents and suppression of gelation during the reaction, as well as compatibility with other resins of the obtained component (B), dielectric properties, low thermal expansion and heat resistance, and among these, the compound represented by the following general formula (b2-1) is more preferred.

[0094] [Chemical formula] (In the formula, R b1 and R b2 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms. X b1 is an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, a single bond, or a divalent group represented by the following general formula (b2-1-1). q1 and q2 are each independently an integer of 0 to 4.)

[0095] R b1 and R b2 Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by include 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, etc. From the viewpoints of compatibility with other resins and suppression of gelation during the reaction, the aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably a methyl group or an ethyl group.

[0096] X b1 Examples of the alkylene group having 1 to 5 carbon atoms represented by include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, a 1,5-pentamethylene group, etc. As the alkylene group, an alkylene group having 1 to 3 carbon atoms is preferable, an alkylene group having 1 or 2 carbon atoms is more preferable, and a methylene group is even more preferable. X b1 Examples of the alkylidene group having 2 to 5 carbon atoms represented by include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group, an isopentylidene group, etc. q1 and q2 are each independently an integer of 0 to 4. From the viewpoints of availability, compatibility with other resins, and suppression of gelation during the reaction, both are preferably integers of 1 to 3, more preferably 1 or 2, and even more preferably 2. From a similar viewpoint, q1+q2 is preferably an integer from 1 to 8, more preferably an integer from 2 to 6, and even more preferably 4. If q1 or q2 is an integer greater than or equal to 2, multiple R b1 Mutual or R b2 They may be the same or they may be different.

[0097] Note X b1 The divalent group represented by the general formula (b2-1-1) is as follows:

[0098] [ka] (In the formula, R b3 and R b4 Each of these is independently an aliphatic hydrocarbon group or halogen atom having 1 to 5 carbon atoms. b2 q3 is an alkylene group with 1 to 5 carbon atoms, an alkylidene group with 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, or a single bond. q3 and q4 are each an integer from 0 to 4. * represents a bonding site.

[0099] R b3 and R b4 The aliphatic hydrocarbon group with 1 to 5 carbon atoms represented by R is an aliphatic hydrocarbon group with 1 to 5 carbon atoms, and the halogen atom is R. b1 It is explained in the same way as in the case of this example. X b2 The alkylene group with 1 to 5 carbon atoms and the alkylidene group with 2 to 5 carbon atoms represented by are: b1 Examples include alkylene groups with 1 to 5 carbon atoms and alkylidene groups with 2 to 5 carbon atoms, which are the same as those represented by [the symbol]. q3 and q4 are each an integer between 0 and 4, and from the viewpoint of availability, both are preferably integers between 0 and 2, more preferably 0 or 1, and even more preferably 0. If q3 or q4 is an integer of 2 or more, multiple R b3 Mutual or R b4 They may be the same or they may be different.

[0100] Among the compounds represented by the above general formula (b2-1), 4,4'-diphenylmethanebismaleimide, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, and 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide are preferred, and 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide is more preferred, from the viewpoint of solubility in organic solvents, suppression of gelation during the reaction, compatibility with other resins of the obtained (B1) component, dielectric properties, low thermal expansion, and heat resistance.

[0101] The modified conjugated diene polymer (B1) preferably has substituents [hereinafter sometimes referred to as "substituents (x)"] in its side chains, which are formed by the reaction of a vinyl group of the conjugated diene polymer (b1) with an N-substituted maleimide group of the maleimide compound (b2). From the viewpoint of compatibility with other resins, dielectric properties, low thermal expansion, and heat resistance, the substituent (x) is preferably a group that includes a structure represented by the following general formula (B1-11) or (B1-12) as a structure derived from the maleimide compound (b2).

[0102] [ka] (In the formula, X B1 is a divalent organic group, * B1 This is a site where the conjugated diene polymer (b1) bonds to carbon atoms derived from vinyl groups in its side chains. B2 (This is a site that bonds to other atoms.)

[0103] In the above general formulas (B1-11) and (B1-12), X B1 The explanation for this is given by X in the general formula (b2-1) above. b1 This is the same as the explanation for [the other topic].

[0104] Furthermore, from the viewpoint of compatibility with other resins, dielectric properties, low thermal expansion, and heat resistance, the substituent (x) more preferably includes one or more structures selected from the group consisting of structures represented by the following general formula (B1-21) and structures represented by the following general formula (B1-22), as structures derived from the maleimide compound (b2).

[0105] [ka] (In the formula, R b1、 R b2 , X b1 The explanations for q1 and q2 are as described in the general formula (b2-1) above. B1 and * B2 The explanation for this is as described in the general formulas (B1-11) and (B1-12) above.

[0106] The modified conjugated diene polymer (B1) preferably has a substituent (x) and a vinyl group (y) in its side chain. The extent to which substituents (x) are present in the modified conjugated diene polymer (B1) can be indicated by the extent to which the vinyl groups of component (b1) have been modified by component (b2) [hereinafter sometimes referred to as the "vinyl group modification rate"]. The vinyl group modification rate is not particularly limited, but from the viewpoint of compatibility with other resins, dielectric properties, low thermal expansion, and heat resistance, it is preferably 20-70%, more preferably 30-60%, and even more preferably 40-50%. Here, the vinyl group modification rate is the value obtained by the method described in the examples. The vinyl group (y) is preferably a 1,2-vinyl group found in the structural unit derived from butadiene.

[0107] The number-average molecular weight of the modified conjugated diene polymer (B1) is not particularly limited, but from the viewpoint of compatibility with other resins, dielectric properties, low thermal expansion, and heat resistance, it is preferably 700 to 6,000, more preferably 800 to 5,000, even more preferably 900 to 4,500, and particularly preferably 1,000 to 4,000.

[0108] [Method for producing component (B1)] The method for reacting the conjugated diene polymer (b1) with the maleimide compound (b2) is not particularly limited. For example, the conjugated diene polymer (b1), the maleimide compound (b2), a reaction catalyst, and an organic solvent can be placed in a reaction vessel and reacted while heating, maintaining temperature, stirring, etc., as necessary to obtain component (B1). The reaction temperature in the above reaction is preferably 70 to 120°C, more preferably 80 to 110°C, and even more preferably 85 to 105°C, from the viewpoint of workability and suppression of gelation during the reaction. Furthermore, the reaction time in the above reaction is preferably 0.5 to 15 hours, more preferably 1 to 10 hours, and even more preferably 3 to 7 hours. However, these reaction conditions can be adjusted as appropriate depending on the type of raw materials used, and are not particularly limited.

[0109] Examples of organic solvents used in the above reaction include alcohol-based solvents such as methanol, ethanol, butanol, butyl cellosolve, ethylene glycol monomethyl ether, and propylene glycol monomethyl ether; ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aromatic hydrocarbon-based solvents such as toluene, xylene, and mesitylene; ester-based solvents such as methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate, and ethyl acetate; and nitrogen atom-containing solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone. Organic solvents may be used individually or in combination of two or more. Among these, toluene is preferred from the viewpoint of resin solubility.

[0110] When the above reaction is carried out in an organic solvent, the total content of the conjugated diene polymer (b1) and maleimide compound (b2) in the reaction solution is not particularly limited, but is preferably 10 to 70% by mass, more preferably 15 to 60% by mass, and even more preferably 20 to 50% by mass. When the total content of the conjugated diene polymer (b1) and maleimide compound (b2) is above the lower limit, a good reaction rate is obtained and productivity tends to be better. Also, when the total content of the conjugated diene polymer (b1) and maleimide compound (b2) is below the upper limit, better solubility is obtained, stirring efficiency is improved, and gelation tends to be further suppressed.

[0111] As the reaction catalyst, those listed as curing accelerator (E) later can be used. Among these, organic peroxides are preferred, and α,α'-bis(t-butylperoxy)diisopropylbenzene is more preferred, from the viewpoint of suppressing gelation during the reaction while obtaining sufficient reactivity. The reaction catalyst may be used alone or in combination of two or more types. The amount of reaction catalyst used is not particularly limited, but is preferably 0.01 to 1.2 parts by mass, more preferably 0.03 to 1.0 parts by mass, and even more preferably 0.05 to 0.8 parts by mass, per 100 parts by mass of the total amount of conjugated diene polymer (b1) and maleimide compound (b2).

[0112] When carrying out the above reaction, the number of moles (M) of side-chain vinyl groups in the conjugated diene polymer (b1) v ) 、 The number of moles of N-substituted maleimide groups in maleimide compound (b2) (M m ) ratio (M m / M v The (B1) component is not particularly limited, but from the viewpoint of compatibility with other resins and suppression of gelation during the reaction, it is preferably 0.01 to 0.5, more preferably 0.02 to 0.4, and even more preferably 0.04 to 0.3.

[0113] (Styrene-based elastomer (B2)) (B2) There are no particular restrictions on the component as long as it is an elastomer having structural units derived from styrene compounds. (B2) Component (B2) may be used alone or in combination of two or more components.

[0114] (B2) Component is preferably one having a styrene-derived structural unit represented by the following general formula (B2-1).

[0115] [ka] (In the formula, R b5 R is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. b6 k is an alkyl group having 1 to 5 carbon atoms. k is an integer from 0 to 5.

[0116] R b5 and R b6 Examples of C1-C5 alkyl groups represented by include methyl, ethyl, and n-propyl groups. Among these, C1-C3 alkyl groups are preferred, C1-C2 alkyl groups are more preferred, and methyl groups are even more preferred. k is preferably an integer between 0 and 2, more preferably 0 or 1, and even more preferably 0.

[0117] (B2) Structural units other than those derived from styrene compounds that component (B2) may have include, for example, structural units derived from butadiene, isoprene, maleic acid, and maleic anhydride. The butadiene-derived structural units and isoprene-derived structural units described above may be hydrogenated. When hydrogenated, the butadiene-derived structural units become structural units that are a mixture of ethylene units and butylene units, and the isoprene-derived structural units become structural units that are a mixture of ethylene units and propylene units.

[0118] As for component (B2), from the viewpoint of dielectric properties, adhesion to conductors, heat resistance, glass transition temperature and low thermal expansion, one or more selected from the group consisting of hydrogenated styrene-butadiene-styrene block copolymers (SEBS, SBBS), hydrogenated styrene-isoprene-styrene block copolymers (SEPS), and styrene-maleic anhydride copolymers (SMA) are preferred, one or more selected from the group consisting of hydrogenated styrene-butadiene-styrene block copolymers (SEBS) and hydrogenated styrene-isoprene-styrene block copolymers (SEPS) are more preferred, and hydrogenated styrene-butadiene-styrene block copolymers (SEBS) are even more preferred.

[0119] In the above-mentioned SEBS, the content of styrene-derived structural units [hereinafter sometimes referred to as "styrene content"] is not particularly limited, but from the viewpoint of dielectric properties, adhesion to conductors, heat resistance, glass transition temperature and low thermal expansion, it is preferably 5 to 80% by mass, more preferably 10 to 75% by mass, even more preferably 15 to 70% by mass, and particularly preferably 20 to 50% by mass.

[0120] The melt flow rate (MFR) of SEBS is not particularly limited, but under measurement conditions of 230°C and a load of 2.16 kgf (21.2 N), it is preferably 0.1 to 20 g / 10 min, more preferably 0.3 to 17 g / 10 min, and even more preferably 0.5 to 15 g / 10 min.

[0121] Examples of commercially available SEBS products include the ToughTec® H series and M series manufactured by Asahi Kasei Corporation, the Septon® series manufactured by Kuraray Co., Ltd., and the Kraton® G polymer series manufactured by Kraton Polymer Japan Co., Ltd.

[0122] The weight-average molecular weight (Mw) of component (B2) is not particularly limited, but is preferably 12,000 to 1,000,000, more preferably 30,000 to 500,000, even more preferably 50,000 to 120,000, and particularly preferably 70,000 to 100,000. The weight-average molecular weight (Mw) is measured in polystyrene equivalent by gel permeation chromatography (GPC).

[0123] [Content of modified conjugated diene polymer (B1) and styrene elastomer (B2)] In the resin composition of this embodiment, when components (B1) and (B2) are used in combination, the content ratio of component (B1) to component (B2) [(B1) / (B2)] is not particularly limited, but from the viewpoint of moldability, compatibility with other resins and dielectric properties, it is preferably 5 / 95 to 70 / 30 by mass, more preferably 10 / 90 to 60 / 40, even more preferably 15 / 85 to 50 / 50, and particularly preferably 20 / 80 to 40 / 60.

[0124] <Content of maleimide compounds or their derivatives (A) and (B), and their respective content percentages> In the resin composition of this embodiment, the content of component (A) is not particularly limited, but is preferably 10 to 90 parts by mass, more preferably 20 to 80 parts by mass, even more preferably 30 to 70 parts by mass, and particularly preferably 35 to 60 parts by mass, based on 100 parts by mass of the total amount of resin components in the resin composition. When the content of component (A) is above the lower limit, the heat resistance, moldability, processability, and flame retardancy tend to be better. Also, when the content of component (A) is below the upper limit, the dielectric properties and moldability tend to be better. In the resin composition of this embodiment, the content of component (B) is not particularly limited, but is preferably 10 to 90 parts by mass, more preferably 20 to 80 parts by mass, even more preferably 30 to 70 parts by mass, and particularly preferably 40 to 65 parts by mass, based on 100 parts by mass of the total amount of resin components in the resin composition. When the content of component (B) is above the lower limit, dielectric properties and moisture resistance tend to be better. Also, when the content of component (B) is below the upper limit, heat resistance, moldability, processability, and flame retardancy tend to be better. Herein, in this specification, "resin component" refers to component (A), component (B), and any resin used as optional. In other words, if the resin composition does not contain any resin, "resin component" refers to component (A) and component (B). If the resin composition contains any resin, "resin component" includes component (A), component (B), and any resin.

[0125] The content ratio of component (A) to component (B) [(A) / (B)] is not particularly limited, but from the viewpoint of compatibility with other resins, dielectric properties, low thermal expansion, and heat resistance, it is preferably 0.3 to 3.0, more preferably 0.4 to 2.5, even more preferably 0.5 to 2.0, particularly preferably 0.6 to 1.5, and most preferably 0.7 to 1.0 by mass. When the content ratio of component (A) to component (B) [(A) / (B)] is above the lower limit, heat resistance, moldability, processability, and flame retardancy tend to be better. Also, when the content ratio of component (A) to component (B) [(A) / (B)] is below the upper limit, dielectric properties tend to be better.

[0126] <Other ingredients> The resin composition of this embodiment may further contain other components depending on the desired performance. Other components include, for example, one or more selected from the group consisting of inorganic fillers (C) [hereinafter sometimes referred to as "component (C)"], flame retardants (D) [hereinafter sometimes referred to as "component (D)"], and curing accelerators (E) [hereinafter sometimes referred to as "component (E)"]. However, the resin composition of this embodiment does not necessarily have to contain one or more selected from the group consisting of inorganic fillers (C), flame retardants (D), and curing accelerators (E), depending on the desired performance. The following details these components.

[0127] (Inorganic filler (C)) The resin composition of this embodiment tends to have improved low thermal expansion, elastic modulus, heat resistance, and flame retardancy by containing an inorganic filler (C). The inorganic filler (C) may be used alone or in combination of two or more types.

[0128] Examples of inorganic fillers (C) include silica, alumina, titanium oxide, mica, beryllium, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay, talc, aluminum borate, and silicon carbide. Among these, silica, alumina, mica, and talc are preferred from the viewpoint of low thermal expansion, elastic modulus, heat resistance, and flame retardancy, silica and alumina are more preferred, and silica is even more preferred. Examples of silica include precipitated silica, which is produced by a wet process and has a high water content, and dry-process silica, which is produced by a dry process and contains almost no bound water. Furthermore, dry-process silica can be further categorized by manufacturing method into crushed silica, fumed silica, fused silica, etc.

[0129] The particle size of the inorganic filler (C) is not particularly limited, but is preferably 0.01 to 20 μm, more preferably 0.1 to 10 μm, even more preferably 0.2 to 1 μm, and most preferably 0.3 to 0.8 μm. Here, the particle size of the inorganic filler (C) refers to the average particle diameter, which is the particle diameter at the point corresponding to 50% of the volume when the cumulative frequency distribution curve by particle diameter is calculated with the total volume of particles set to 100%. The particle size of the inorganic filler (C) can be measured using a particle size distribution analyzer that uses laser diffraction scattering or the like. The inorganic filler (C) can take various shapes, such as spherical or crushed, with a spherical shape being preferred.

[0130] When the resin composition of this embodiment contains an inorganic filler (C), the amount of inorganic filler (C) in the resin composition is not particularly limited, but from the viewpoint of low thermal expansion, elastic modulus, heat resistance and flame retardancy, it is preferably 5 to 70% by mass, more preferably 15 to 65% by mass, even more preferably 20 to 60% by mass, particularly preferably 30 to 55% by mass, and most preferably 40 to 50% by mass, relative to the total solid content (100% by mass) of the resin composition.

[0131] If the resin composition of this embodiment contains an inorganic filler (C), a coupling agent may be used to improve the dispersibility of the inorganic filler (C) and its adhesion to organic components. Examples of coupling agents include silane coupling agents and titanate coupling agents. When using a coupling agent, the surface treatment method for the inorganic filler (C) may be an integral blend treatment method in which the inorganic filler (C) is blended into the resin composition and then the coupling agent is added, or it may be a method in which the inorganic filler (C) is pre-treated with the coupling agent by dry or wet processes. Among these, from the viewpoint of more effectively expressing the characteristics of the inorganic filler (C), the method of pre-treating the inorganic filler (C) with the coupling agent by dry or wet processes is preferred. The inorganic filler (C) may be pre-dispersed in an organic solvent to form a slurry before being mixed with the other components, in order to improve its dispersibility in the resin composition.

[0132] (Flame retardant (D)) The resin composition of this embodiment tends to have improved flame retardancy due to the inclusion of a flame retardant (D). Flame retardant (D) may be used alone or in combination of two or more types. Furthermore, a flame retardant aid may be included as needed.

[0133] Examples of flame retardants (D) include phosphorus-based flame retardants, metal hydrates, and halogen-based flame retardants. From an environmental perspective, phosphorus-based flame retardants and metal hydrates are preferred.

[0134] -Phosphorus-based flame retardant- The phosphorus-based flame retardant is not particularly limited as long as it contains phosphorus atoms and is generally used as a flame retardant; it may be an inorganic or organic phosphorus-based flame retardant. From an environmental standpoint, phosphorus-based flame retardants that do not contain halogen atoms are preferred. From the viewpoint of dielectric properties, adhesion to conductors, heat resistance, glass transition temperature, low thermal expansion, and flame retardancy, organic phosphorus-based flame retardants are preferred. Examples of inorganic phosphorus-based flame retardants include red phosphorus; ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and polyammonium phosphate; inorganic nitrogen-containing phosphorus compounds such as phosphate amides; phosphoric acid; and phosphine oxide. Examples of organic phosphorus-based flame retardants include aromatic phosphate esters, monosubstituted phosphonic acid diesters, disubstituted phosphinic acid esters, metal salts of disubstituted phosphinic acid, organic nitrogen-containing phosphorus compounds, and cyclic organophosphorus compounds. Among these, aromatic phosphate ester compounds and metal salts of disubstituted phosphinic acid are preferred. Examples of metal salts include lithium salts, sodium salts, potassium salts, calcium salts, magnesium salts, aluminum salts, titanium salts, and zinc salts. Among these, aluminum salts are preferred. Furthermore, among organic phosphorus-based flame retardants, aromatic phosphate esters are preferred.

[0135] Examples of aromatic phosphate esters include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl di-2,6-xylenyl phosphate, resorcinol bis(diphenyl phosphate), 1,3-phenylene bis(di-2,6-xylenyl phosphate), bisphenol A-bis(diphenyl phosphate), and 1,3-phenylene bis(diphenyl phosphate). Examples of monosubstituted phosphonic acid diesters include divinyl phenylphosphonate, diallyl phenylphosphonate, and bis(1-butenyl) phenylphosphonate. Examples of disubstituted phosphinate esters include phenyl diphenylphosphinate and methyl diphenylphosphinate. Examples of metal salts of disubstituted phosphinic acids include metal salts of dialkylphosphinic acid, diallylphosphinic acid, divinylphosphinic acid, and diarylphosphinic acid. Aluminum salts are preferred among these metal salts. Examples of organic nitrogen-containing phosphorus compounds include phosphazene compounds such as bis(2-allylphenoxy)phosphazene and dicresylphosphazene; melamine phosphate; melamine pyrophosphate; melamine polyphosphate; and melamine polyphosphate. Examples of cyclic organophosphorus compounds include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide. Among these, aromatic phosphate esters and metal salts of disubstituted phosphinic acids are preferred, 1,3-phenylenebis(di-2,6-xylenyl phosphate) and aluminum salts of dialkylphosphinic acids are more preferred, and aluminum trisdiethylphosphinate is even more preferred.

[0136] -Metal hydrate- Examples of metal hydrates include aluminum hydroxide hydrate and magnesium hydroxide hydrate.

[0137] -Halogen-based flame retardant- Examples of halogen-based flame retardants include chlorine-based flame retardants and bromine-based flame retardants. Examples of chlorine-based flame retardants include chlorinated paraffins.

[0138] When the resin composition of this embodiment contains a flame retardant (D), the amount of flame retardant (D) is not particularly limited, but is preferably 1 to 15 parts by mass, more preferably 3 to 10 parts by mass, and even more preferably 4 to 8 parts by mass, based on 100 parts by mass of the total amount of resin components in the resin composition. When the amount of flame retardant (D) is above the lower limit, the flame retardancy tends to be better. Also, when the amount of flame retardant (D) is below the upper limit, the moldability, high adhesion to conductors, heat resistance, and high glass transition temperature tend to be better.

[0139] (Curing accelerator (E)) The resin composition of this embodiment, by containing a curing accelerator (E), exhibits improved curability, and tends to have improved dielectric properties, heat resistance, adhesion to conductors, elastic modulus, and glass transition temperature. The curing accelerator (E) may be used alone or in combination of two or more types.

[0140] Examples of curing accelerators (E) include acidic catalysts such as p-toluenesulfonic acid; amine compounds such as triethylamine, pyridine, and tributylamine; imidazole compounds such as methylimidazole and phenylimidazole; isocyanate-mask imidazole compounds such as the addition reaction product of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole; tertiary amine compounds; quaternary ammonium compounds; phosphorus compounds such as triphenylphosphine; organic peroxides such as dicumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexine-3, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, t-butylperoxyisopropyl monocarbonate, and α,α'-bis(t-butylperoxy)diisopropylbenzene; and carboxylates of manganese, cobalt, zinc, etc. Among these, imidazole compounds, isocyanate-masked imidazole compounds, organic peroxides, and carboxylates are preferred from the viewpoint of heat resistance, glass transition temperature, and storage stability, organic peroxides are more preferred, and dicumyl peroxides are even more preferred.

[0141] When the resin composition of this embodiment contains a curing accelerator (E), the content of the curing accelerator (E) is not particularly limited, but is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 8 parts by mass, even more preferably 0.1 to 6 parts by mass, and particularly preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the total amount of resin components in the resin composition. When the content of the curing accelerator (E) is above the lower limit, dielectric properties, heat resistance, adhesion to conductors, elastic modulus, and glass transition temperature tend to be better. Also, when the content of the curing accelerator (E) is below the upper limit, storage stability tends to be better.

[0142] The resin composition of this embodiment may further contain, if necessary, one or more selected from the group consisting of resin materials other than the above-mentioned components, antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, pigments, colorants, lubricants, and other additives. Each of these may be used individually or in combination of two or more. Furthermore, the amount used is not particularly limited and may be used as needed, within a range that does not impair the effects of this embodiment.

[0143] (Organic solvents) The resin composition of this embodiment may contain an organic solvent, from the viewpoint of facilitating handling and facilitating the production of the prepreg described later. Organic solvents may be used individually or in combination of two or more types. In this specification, a resin composition containing an organic solvent may be referred to as a resin varnish.

[0144] Examples of organic solvents include alcohol-based solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether-based solvents such as tetrahydrofuran; aromatic hydrocarbon-based solvents such as toluene, xylene, and mesitylene; nitrogen-containing solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; sulfur-containing solvents such as dimethyl sulfoxide; and ester-based solvents such as γ-butyrolactone. Among these, from the viewpoint of solubility, alcohol-based solvents, ketone-based solvents, nitrogen atom-containing solvents, and aromatic hydrocarbon-based solvents are preferred, aromatic hydrocarbon-based solvents are more preferred, and toluene is even more preferred.

[0145] When the resin composition of this embodiment contains an organic solvent, the solid content concentration of the resin composition is not particularly limited, but is preferably 30 to 90% by mass, more preferably 35 to 80% by mass, and even more preferably 40 to 60% by mass. When the solid content concentration is within the above range, the handling of the resin composition becomes easier, and the impregnation into the substrate and the appearance of the manufactured prepreg tend to be better. In addition, it becomes easier to adjust the solid content concentration of the resin in the prepreg, as described later, and it tends to be easier to manufacture a prepreg with a desired thickness.

[0146] The resin composition of this embodiment can be produced by mixing component (A) and component (B), and other components used in combination as needed, in a known manner. In this case, each component may be dissolved or dispersed while stirring. The mixing order, temperature, time, and other conditions are not particularly limited and can be set arbitrarily depending on the type of raw materials, etc.

[0147] The resin composition of this embodiment is not particularly limited, but in the compatibility evaluation in the examples described later, it is preferable that there is no macroscopic phase separation or precipitate after being left for 1 day, more preferably that there is no macroscopic phase separation or precipitate after being left for 2 days, and even more preferably that there is no macroscopic phase separation or precipitate after being left for 7 days.

[0148] The relative permittivity (Dk) of the cured resin composition of this embodiment at 10 GHz is not particularly limited, but is preferably 3.0 or less, more preferably 2.9 or less, and even more preferably 2.8 or less. A smaller relative permittivity (Dk) is preferable, and there is no particular limit to its lower limit, but considering the balance with other physical properties, it may be, for example, 2.4 or more, or 2.5 or more. The relative permittivity (Dk) mentioned above is a value obtained in accordance with the cavity resonator perturbation method, and more specifically, it is a value measured by the method described in the examples.

[0149] The dielectric loss tangent (Df) of the cured resin composition of this embodiment at 10 GHz is not particularly limited, but is preferably 0.0050 or less, more preferably 0.0040 or less, even more preferably 0.0030 or less, particularly preferably 0.0025 or less, and most preferably 0.0020 or less. The smaller the dielectric loss tangent (Df), the better. There is no particular limit to its lower limit, but considering the balance with other physical properties, it may be, for example, 0.0010 or more, or 0.0012 or more. The above dielectric loss tangent (Df) is a value obtained in accordance with the cavity resonator perturbation method, and more specifically, it is a value measured by the method described in the examples.

[0150] [Prepreg] The prepreg of this embodiment is a prepreg containing the resin composition of this embodiment or a semi-cured product of the resin composition. In other words, the prepreg of this embodiment can also be said to contain the resin composition of this embodiment. In this specification, "contains" means formed at least through a state of containing the composition. The prepreg of this embodiment, for example, contains the resin composition of this embodiment or a semi-cured product of the resin composition and a sheet-like fibrous substrate. The sheet-like fibrous substrate is not particularly limited, but it is preferably a sheet-like fibrous reinforcing substrate used for the purpose of reinforcing a prepreg. As the sheet-like fiber base material contained in the prepreg of the present embodiment, known sheet-like fiber base materials used in various laminate boards for electrical insulating materials can be used. Examples of the material of the sheet-like fiber base material include inorganic fibers such as E glass, D glass, S glass, and Q glass; organic fibers such as polyimide, polyester, and tetrafluoroethylene; and mixtures thereof. These sheet-like fiber base materials have shapes such as woven fabrics, non-woven fabrics, rovings, chopped strand mats, and surfacing mats, for example. The thickness of the sheet-like fiber base material is not particularly limited, but is, for example, 0.02 to 0.5 mm. The sheet-like fiber base material may be surface-treated with a coupling agent or the like, or may be mechanically fibrillated, from the viewpoints of the impregnation property of the resin composition and the heat resistance, moisture absorption resistance, and workability when made into a laminate.

[0151] The prepreg of the present embodiment can be produced, for example, by impregnating or coating the sheet-like fiber base material with the resin composition of the present embodiment and drying it as necessary. As a method of impregnating or coating the resin composition on the sheet-like fiber base material, for example, a hot melt method, a solvent method, or the like can be adopted.

[0152] The hot melt method is a method of impregnating or coating a resin composition that does not contain an organic solvent on a sheet-like fiber base material. As one aspect of the hot melt method, there is a method of once coating the resin composition on a coating paper with good peelability and laminating the coated resin composition on the sheet-like fiber base material. Another aspect of the hot melt method is a method of directly applying the resin composition to the sheet-like fiber base material using a die coater or the like.

[0153] The solvent method is a method of impregnating or coating a resin composition containing an organic solvent on a sheet-like fiber base material. Specifically, for example, there is a method of immersing the sheet-like fiber base material in a resin composition containing an organic solvent and then drying it. As the drying conditions of the solvent method, for example, in a drying furnace, heating can be carried out at a temperature of 80 to 200 °C for 1 to 30 minutes. By drying, the organic solvent is removed and the resin composition is semi-cured (B-staged) to obtain the prepreg of the present embodiment.

[0154] The solid content concentration derived from the resin composition in the prepreg of the present embodiment is not particularly limited, but is preferably 30 to 90% by mass. When the solid content concentration derived from the resin composition in the prepreg is within the above range, better formability tends to be obtained when it is made into a laminate.

[0155] [Resin film] The resin film of the present embodiment contains the resin composition of the present embodiment or a semi-cured product of the resin composition. That is, it can be said that the resin film of the present embodiment is formed by containing the resin composition of the present embodiment. The resin film of the present embodiment can be produced, for example, by applying a resin composition containing an organic solvent, that is, a resin varnish, to a support and drying it by heating. Examples of the support include films of polyolefins such as polyethylene, polypropylene, and polyvinyl chloride; films of polyesters such as polyethylene terephthalate [hereinafter sometimes referred to as "PET"], polyethylene naphthalate, etc.; various plastic films such as polycarbonate films and polyimide films; metal foils such as copper foils and aluminum foils; release papers, and the like. The support may be subjected to surface treatment such as mat treatment or corona treatment. Further, the support may be subjected to a release treatment with a silicone resin-based release agent, an alkyd resin-based release agent, a fluororesin-based release agent, or the like. The thickness of the support is not particularly limited, but is preferably 10 to 150 μm, more preferably 20 to 100 μm, and still more preferably 25 to 50 μm.

[0156] For applying resin varnish, coating devices known to those skilled in the art, such as comma coaters, bar coaters, kiss coaters, roll coaters, gravure coaters, and die coaters, can be used. These coating devices should be appropriately selected depending on the film thickness to be formed. The drying conditions after applying the resin composition can be appropriately determined depending on the content and boiling point of the organic solvent. For example, in the case of a resin varnish containing 40-60% by mass of an aromatic hydrocarbon solvent, a resin film can be suitably formed by drying it at 50-200°C for about 3-10 minutes.

[0157] [Laminated board] The laminate of this embodiment comprises a cured product of the resin composition of this embodiment or a cured product of a prepreg, and a metal foil. In other words, the laminate of this embodiment can also be said to contain the resin composition or prepreg of this embodiment and a metal foil. Laminates containing metal foil are sometimes referred to as metal-clad laminates. The metal of the metal foil is not particularly limited, but from the viewpoint of conductivity, copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, or alloys containing one or more of these metal elements are preferred, copper and aluminum are more preferred, and copper is even more preferred.

[0158] The laminate of this embodiment can be manufactured, for example, by placing metal foil on one or both sides of the prepreg of this embodiment, and then heat-pressure molding it. In this case, only one prepreg may be used, or two or more prepregs may be laminated together. The conditions for heat-pressure molding are not particularly limited, but for example, the temperature can be 100 to 300°C, the pressure 0.2 to 10 MPa, and the time 0.1 to 5 hours. Alternatively, the heat-pressure molding may be carried out using a method that maintains a vacuum state for 0.5 to 5 hours using a vacuum press or the like.

[0159] [Printed wiring board] The printed circuit board of this embodiment has one or more selected from the group consisting of a cured product of the resin composition of this embodiment, a cured product of the prepreg of this embodiment, and a laminate of this embodiment. In other words, the printed circuit board of this embodiment can also be said to contain one or more selected from the group consisting of the resin composition of this embodiment, the prepreg of this embodiment, and the laminate of this embodiment. The printed circuit board of this embodiment has a structure containing at least a cured product of the resin composition of this embodiment, a cured product of the prepreg of this embodiment, or a laminate of this embodiment, and a conductor circuit layer. The printed circuit board of this embodiment can be manufactured by forming conductive circuits on one or more materials selected from the group consisting of a cured resin composition of this embodiment, a cured prepreg of this embodiment, a cured resin film of this embodiment, and a laminate of this embodiment, using a known method. Furthermore, a multilayer printed circuit board can be manufactured by performing a multilayer bonding process as needed. Conductor circuits can be formed by, for example, drilling holes, metal plating, etching metal foil, etc., as appropriate.

[0160] [Semiconductor Packages] The semiconductor package of this embodiment comprises the printed circuit board of this embodiment and semiconductor elements. The semiconductor package of this embodiment can be manufactured, for example, by mounting semiconductor chips, memory, etc., on the printed circuit board of this embodiment using a known method.

[0161] The maleimide resin composition, prepreg, laminate, resin film, printed circuit board, and semiconductor package of this embodiment are suitable for electronic equipment that handles high-frequency signals of 10 GHz or higher. In particular, the printed circuit board is useful as a printed circuit board for millimeter-wave radar. [Examples]

[0162] The embodiment will be described in detail below with reference to examples. However, this embodiment is not limited to the following examples.

[0163] In each example, the number average molecular weight was measured by the following procedure. (Method for measuring number average molecular weight) The number average molecular weight was converted from a calibration curve using standard polystyrene by gel permeation chromatography (GPC). The calibration curve was approximated by a cubic equation using standard polystyrene: TSK standard POLYSTYRENE (Type; A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) [manufactured by Tosoh Corporation, trade name]. The measurement conditions of GPC are shown below. Apparatus: High-speed GPC apparatus HLC-8320GPC Detector: Ultraviolet absorption detector UV-8320 [manufactured by Tosoh Corporation] Column: Guard column; TSK Guardcolumn SuperHZ-L + Column; TSKgel SuperHZM-N + TSKgel SuperHZM-M + TSKgel SuperH-RC (all manufactured by Tosoh Corporation, trade name) Column size: 4.6 × 20 mm (guard column), 4.6 × 150 mm (column), 6.0 × 150 mm (reference column) Eluent: Tetrahydrofuran Sample concentration: 10 mg / 5 mL Injection volume: 25 μL Flow rate: 1.00 mL / min Measurement temperature: 40 °C

[0164] (Measurement of vinyl group modification rate) In the production examples described below, for the solution containing components (b1) and (b2) before the start of the reaction and the solution after the reaction, GPC was measured by the above method, and the peak area derived from component (b2) before and after the reaction was determined. Next, the vinyl group modification rate of component (b2) was calculated by the following formula. The vinyl group modification rate corresponds to the decrease rate of the peak area derived from component (b2) due to the reaction. Vinyl group modification rate = [(peak area derived from component (b2) before reaction) - (peak area derived from component (b2) after reaction)] × 100 / (peak area derived from component (b2) before reaction)

[0165] [Production of Modified Conjugated Diene Polymer (B1)] Manufacturing Examples 1-5 In a 2 L glass flask container equipped with a thermometer, reflux condenser, and stirring device, the amounts of component (b1), component (b2), organic peroxide, and toluene as an organic solvent shown in Table 1 were added. Then, under a nitrogen atmosphere, component (b1) and component (b2) were reacted at 90-100°C for 5 hours with stirring to obtain solutions of modified conjugated diene polymers B1-1 to B1-5 with a solid content concentration of 35% by mass.

[0166] [Table 1]

[0167] The details of each component listed in Table 1 are as follows: [(b1) component] Polybutadiene 1:1,2-polybutadiene homopolymer, number-average molecular weight = 3,200, vinyl group content = 90% or more Polybutadiene 2:1,2-polybutadiene homopolymer, number-average molecular weight = 2,100, vinyl group content = 90% or more Polybutadiene 3:1,2-polybutadiene homopolymer, number-average molecular weight = 1,200, vinyl group content = 85% or more [(b2) component] • Bismaleimide compound 1: 4,4'-diphenylmethanebismaleimide • Bismaleimide compound 2: 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane • Bismaleimide compound 3: 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide [Reaction catalyst] • Organic peroxide: α,α'-bis(t-butylperoxy)diisopropylbenzene

[0168] [Manufacturing of resin compositions] Examples 1-8, Comparative Examples 1-2 Each component listed in Table 2 was combined with toluene according to the proportions listed in Table 2, and the mixture was stirred and mixed while heating at 25°C or 50-80°C to prepare a resin composition with a solid content of approximately 50% by mass. In Table 2, the unit of the proportion of each component is parts by mass, and in the case of a solution, it means parts by mass on a solid content basis.

[0169] [Manufacturing of resin films and resin sheets with copper foil on both sides] The resin compositions obtained in each example were applied to a 38 μm thick PET film (manufactured by Teijin Limited, product name: G2-38), and then heated and dried at 170°C for 5 minutes to produce a B-stage resin film. After peeling this resin film from the PET film, it was crushed to obtain a B-stage resin powder, which was then placed into a Teflon® sheet die-cut to a size of 1 mm thick × 50 mm long × 35 mm wide. Next, 18 μm thick low-profile copper foil (manufactured by Mitsui Mining & Smelting Co., Ltd., product name: 3EC-VLP-18) was placed above and below the Teflon® sheet containing the resin powder to obtain a laminate before heat and pressure molding. The low-profile copper foil was placed with its M-side facing the resin powder. Subsequently, the laminate was heat and pressure molded at a temperature of 230°C, a pressure of 2.0 MPa, and a time of 120 minutes to mold and harden the resin powder into a resin plate, thereby producing a double-sided copper foil-coated resin plate. The thickness of the resin portion of the obtained double-sided copper foil-covered resin plate was 1 mm.

[0170] [Evaluation methods and measurement methods] The resin compositions and double-sided copper foil-coated resin plates obtained in the above examples and comparative examples were used for the following measurements and evaluations. The results are shown in Table 2.

[0171] (1. Method for evaluating the compatibility of resin compositions) The resin compositions obtained in each example were visually observed, and their compatibility was evaluated according to the following criteria. A: Even after being left for more than a week, no macroscopic phase separation or precipitates were observed. B: After being left for one day, macroscopic phase separation or precipitates were observed.

[0172] (2. Method for measuring minimum melt viscosity) After grinding the resin powder obtained in each example in a mortar, approximately 0.6 g was weighed and formed into a 20 mm diameter disc-shaped tablet using a tablet molder. Subsequently, using this tablet as a measurement sample, the minimum melt viscosity was measured using a rheometer (Rheometric, product name: ARES-2K STD-FCO-STD) under the conditions of a heating rate of 3°C / min, a load of 0.2 N, and a measurement temperature range of 50 to 200°C.

[0173] (3. Measurement methods for relative permittivity and dielectric loss tangent) The double-sided copper foil-covered resin plates obtained in each example were immersed in a 10% by mass solution of ammonium persulfate (manufactured by Mitsubishi Gas Chemical Company, Inc.), a copper etching solution, to remove the copper foil and prepare 2 mm × 50 mm test specimens. Subsequently, the relative permittivity (Dk) and dielectric loss tangent (Df) of the test specimens were measured at 10 GHz in an ambient temperature of 25°C, in accordance with the cavity resonator perturbation method.

[0174] (4. Method for measuring thermal expansion coefficient) For each example, the copper foil on both sides of the double-sided copper foil-covered resin plate was removed by etching to prepare a 5mm square test specimen. Next, the thermal expansion coefficient of the above test specimen was measured using a thermomechanical measuring device (TMA) (manufactured by T.A. Instrument Japan Co., Ltd., product name: Q400) in accordance with the IPC (The Institute for Interconnecting and Packaging Electronic Circuits) standard. The thermal expansion coefficient was the thermal expansion coefficient in the thickness direction of the resin plate, and was taken as the average thermal expansion coefficient over a temperature range of 30 to 120°C.

[0175] (5. Method for measuring peel strength) The copper foil of the double-sided copper foil-coated resin plates obtained in each example was processed into a 5mm wide straight line by etching, and then dried at 105°C for 1 hour to prepare the test specimen. Next, using a small benchtop testing machine (manufactured by Shimadzu Corporation, product name: EZ-Test), the peel strength was measured when the copper foil, which was the straight line of the test specimen, was peeled off at a speed of 50mm / min in a 90° direction, in accordance with JIS C6481.

[0176] (6. Method for evaluating heat resistance) The copper foil on both sides of the double-sided copper foil-covered resin plates obtained in each example was removed by etching to prepare 40mm x 40mm test specimens. These test specimens were then treated using a pressure cooker (Hirayama Seisakusho Co., Ltd., product name: HA-300M) at 121°C and 0.11 MPa. After treatment, the test specimens were immersed in a molten solder bath at 288°C for 20 seconds, and their appearance was visually inspected to evaluate their heat resistance according to the following criteria. A: No swelling was observed. B: A bulge was observed.

[0177] [Table 2]

[0178] The materials listed in Table 2 are as follows: [(A) component] -(A1) component- • Maleimide compound A-1: ​​4,4'-diphenylmethanebismaleimide (molecular weight 358.35) Maleimide compound A-2: 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane (molecular weight 570.60) Maleimide compound A-3: 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide (molecular weight 442.51) -(A2) Component- • Maleimide compound A-4: Maleimide compound having a biphenylaralkyl skeleton (manufactured by Nippon Kayaku Co., Ltd., trade name "MIR-3000") (molecular weight 725) • Maleimide compound A-5: Maleimide compound containing a hydrocarbon group (manufactured by Showa Denko Materials Co., Ltd., product name "SFR-2300MR-M") (number average molecular weight 8,000) • Maleimide compound A-6: Aromatic bismaleimide compound containing an indane ring (number-average molecular weight 1,200)

[0179] [(B) Component] Modified conjugated diene polymers B1-1 to B1-5: Modified conjugated diene polymers B1-1 to B1-5 obtained in Production Examples 1 to 5 • Conjugated diene polymer: 1,2-polybutadiene homopolymer, number average molecular weight = 3,200, vinyl group content = 90% or more • Styrene-based elastomer B2-1: Styrene-ethylene-butylene-styrene (SEBS) copolymer, styrene / ethylene-butylene ratio = 42 / 58 (by mass), manufactured by Asahi Kasei Corporation, product name "ToughTec H1051" • Styrene-based elastomer B2-2: Styrene-ethylene-butylene-styrene (SEBS) copolymer, styrene / ethylene-butylene ratio = 30 / 70 (by mass), manufactured by Asahi Kasei Corporation, product name "ToughTec M1913"

[0180] As is clear from the results shown in Table 2, the resin compositions obtained in Examples 1 to 8 of this embodiment had reduced minimum melt viscosity. Furthermore, the cured products made using these resin compositions exhibited excellent heat resistance and low thermal expansion, as well as excellent dielectric properties in the high frequency band of 10 GHz. On the other hand, the resin compositions of Comparative Example 1 and Comparative Example 2 did not sufficiently reduce the minimum melt viscosity. [Industrial applicability]

[0181] The resin composition of this embodiment has a reduced minimum melt viscosity, and the cured product made from this resin composition exhibits excellent dielectric properties in high-frequency bands of 10 GHz or higher. Therefore, it is useful for printed circuit boards used in fifth-generation mobile communication system (5G) antennas that use radio waves in frequency bands exceeding 6 GHz and millimeter-wave radars that use radio waves in frequency bands of 30 to 300 GHz.

Claims

1. (A) One or more selected from the group consisting of maleimide compounds having one or more N-substituted maleimide groups and derivatives thereof, (B) A polymer having a hydrocarbon chain or polyether chain in its main chain, It contains, The above-mentioned component (A) is, (A1) Maleimide compounds having one or more N-substituted maleimide groups, with a molecular weight of 200 or more and less than 600, and (A2) A maleimide compound having one or more N-substituted maleimide groups, with a molecular weight of 600 or more and 10,000 or less, A maleimide resin composition in which component (B) is a polymer having hydrocarbon chains in its main chain, wherein (b1) a conjugated diene polymer having vinyl groups in its side chains is modified with (b2) a maleimide compound having two or more N-substituted maleimide groups to form a modified conjugated diene polymer (B1).

2. The maleimide resin composition according to claim 1, wherein the (A1) component is an aromatic bismaleimide compound.

3. The maleimide resin composition according to claim 1 or 2, wherein the (A2) component is a maleimide compound containing an alicyclic hydrocarbon group.

4. The maleimide resin composition according to claim 3, wherein the alicyclic hydrocarbon group is included as part of an indan ring.

5. The maleimide resin composition according to any one of claims 1 to 4, further comprising an inorganic filler (C).

6. The maleimide resin composition according to any one of claims 1 to 5, wherein the content ratio of component (A1) to component (A2) [(A1) / (A2)] is 5 / 95 to 50 / 50 by mass.

7. The maleimide resin composition according to any one of claims 1 to 6, wherein the (B1) component has substituents on its side chain formed by the reaction of a vinyl group of the (b1) component and an N-substituted maleimide group of the (b2) component.

8. The maleimide resin composition according to any one of claims 1 to 7, wherein the (b1) component is polybutadiene having a 1,2-vinyl group.

9. The maleimide resin composition according to any one of claims 1 to 8, wherein the content ratio of component (A) to component (B) [(A) / (B)] is 0.3 to 3.0 by mass.

10. A prepreg containing the maleimide resin composition according to any one of claims 1 to 9 or a semi-cured product of the maleimide resin composition.

11. A laminate having a cured maleimide resin composition according to any one of claims 1 to 9 or a cured prepreg according to claim 10, and a metal foil.

12. A resin film containing the maleimide resin composition according to any one of claims 1 to 9 or a semi-cured product of the maleimide resin composition.

13. A printed circuit board comprising one or more selected from the group consisting of a cured maleimide resin composition according to any one of claims 1 to 9, a cured prepreg according to claim 10, and a laminate according to claim 11.

14. A semiconductor package having a printed circuit board according to claim 13 and a semiconductor element.

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