Resin compositions, prepregs, laminates, resin films, multilayer printed circuit boards, antenna devices, and antenna modules

Abstract

To provide a resin composition which is thermally expand at a low level while suppressing the change of a specific dielectric constant (Dk), a prepreg using the resin composition, a laminated plate, a resin film, a multilayer printed wiring board, an antenna device and an antenna module.SOLUTION: There are provided a resin composition which is blended with (A) a thermosetting resin, (B) a titanium-based inorganic filler, and (C) a siloxane compound having a reactive group; a prepreg using the resin composition; a laminated plate; a resin film; a multilayer printed wiring board; an antenna device; and an antenna module.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This embodiment relates to resin compositions, prepregs, laminates, resin films, multilayer printed circuit boards, antenna devices, and antenna modules. [Background technology]

[0002] In recent years, the proliferation of mobile devices such as smartphones, along with technological advancements such as IoT (Internet of Things), has led to an increase in home appliances and electronic devices with wireless communication capabilities. This has resulted in increased communication traffic on wireless networks, raising concerns about a potential decline in communication speed and quality. To solve this problem, development of the fifth-generation mobile communication system (hereinafter sometimes referred to as "5G") is underway and is already being used. In 5G, advanced beamforming and spatial multiplexing are performed using multiple antenna elements, and in addition to the conventionally used 6GHz frequency band signals, higher frequency millimeter-wave band signals of tens of GHz are used. As a result, faster communication speeds and improved communication quality are expected. On the other hand, since mobile devices such as smartphones are required to be miniaturized, it is also necessary to miniaturize the antenna module, and it is widely known that the dielectric constant (Dk) of the substrate needs to be increased in order to achieve miniaturization of the antenna module.

[0003] Furthermore, various components such as metal layers are arranged on the substrate for the antenna module. In this case, warping may occur due to the difference in thermal expansion coefficients between the substrate and the metal layer. Since warping can lead to problems such as poor connections between materials, it is desirable to suppress it.

[0004] Patent Document 1 discloses a resin composition that provides molded articles with excellent dielectric properties and dimensional stability, comprising a liquid crystal polymer and a filler made of a composite oxide containing Ba, Sm, and Ti. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2010-031256 [Overview of the project] [Problems that the invention aims to solve]

[0006] The technology described in Patent Document 1 uses a liquid crystal polymer, which has excellent heat resistance and processability, as the resin for the antenna substrate, while also using a composite oxide containing high dielectric fillers such as Ba, Sm, and Ti to increase the dielectric strength of the substrate. Furthermore, it has been shown that the coefficient of linear expansion of the cured resin composition obtained using the above composite oxide is smaller than that of the cured resin composition obtained using other composite oxides.

[0007] Methods to further reduce the thermal expansion of substrates for antenna modules include, for example, changing the type of high-dielectric filler as described in Patent Document 1, or increasing the amount of high-dielectric filler used. However, substrates for antenna modules are designed with a specific dielectric constant (Dk) value, taking into account the balance of various physical properties, and the product is constructed based on that design value. If the type or amount of high-dielectric filler is changed in a product designed in this way, the dielectric constant (Dk) of the resulting substrate will deviate from the design value. In that case, the material cannot be applied to existing products. Furthermore, changing the design value of the dielectric constant (Dk) necessitates a complete reassessment of the product configuration suitable for that dielectric constant (Dk), which significantly increases development costs.

[0008] In view of the current situation, this embodiment aims to provide a resin composition with low thermal expansion while suppressing changes in relative permittivity (Dk), a prepreg, a laminate, a resin film, a multilayer printed circuit board, an antenna device, and an antenna module using the resin composition. [Means for solving the problem]

[0009] As a result of further investigations to solve the above problems, the inventors have found that the problems can be solved by the following embodiment. In other words, this embodiment relates to the following [1] to

[16] . [1] (A) Thermosetting resin and (B) Titanium-based inorganic filler, (C) Siloxane compound having a reactive group, A resin composition comprising the following: [2](B)Average particle size of titanium-based inorganic filler (D 50 The resin composition described in [1] above, wherein the diameter is 0.1 to 20 μm. [3](B) The resin composition according to [1] or [2] above, wherein the relative permittivity (Dk) of the titanium-based inorganic filler at 10 GHz is 10 to 3,000. [4](B) The resin composition according to any one of [1] to [3] above, wherein the titanium-based inorganic filler is a titanate. [5] The resin composition according to [4] above, wherein the titanate is one or more selected from the group consisting of barium titanate, potassium titanate, calcium titanate, strontium titanate, lead titanate, and aluminum titanate. [6](C) The resin composition according to any one of [1] to [5] above, wherein the siloxane compound having a reactive group is an amino-modified siloxane compound having primary amino groups at both ends. [7] A resin composition according to any one of [1] to [6] above, obtained by reacting (C) a siloxane compound having a reactive group with (A) a thermosetting resin and then blending them. [8] The resin composition according to any one of [1] to [7] above, wherein the (A) thermosetting resin is one or more selected from the group consisting of maleimide compounds having one or more N-substituted maleimide groups and derivatives thereof. [9] The resin composition according to any one of [1] to [8] above, wherein the relative permittivity (Dk) of the cured product at 20 GHz is 2 to 50.

[10] A resin composition according to any of [1] to [9] above, for use in an antenna module.

[11] A prepreg containing any of the resin compositions described in [1] to

[10] above.

[12] A laminate containing the prepreg described in

[11] above and a metal foil.

[13] A resin film containing any of the resin compositions described in [1] to

[10] above.

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

[11] above, the laminate described in

[12] above, and the resin film described in

[13] above.

[15] An antenna device comprising the multilayer printed circuit board described in

[14] above.

[16] An antenna module comprising the antenna device described in

[15] above and a power supply circuit. [Effects of the Invention]

[0010] According to this embodiment, it is possible to provide a resin composition with low thermal expansion while suppressing changes in relative permittivity (Dk), a prepreg using the resin composition, a laminate, a resin film, a multilayer printed circuit board, an antenna device, and an antenna module. [Modes for carrying out the invention]

[0011] In this specification, numerical ranges indicated using "~" represent a range that includes the numbers before and after "~" as the minimum and maximum values, respectively. For example, the notation "X~Y" (where X and Y are real numbers) means a range of numbers that are greater than or equal to X and less than or equal to Y. In this specification, the phrase "greater than or equal to X" means X and numbers greater than X. In this specification, the phrase "less than or equal to Y" means Y and numbers less than Y. 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 lower or upper limits of those ranges may be replaced with the values ​​shown in the examples.

[0012] 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. In this specification, "resin composition" includes mixtures of the components described below, and semi-cured products of said mixtures.

[0013] In this specification, "solids" refers to the non-volatile components excluding volatile substances such as solvents, and represents the components that remain without volatilization when the resin composition is dried. This includes liquid, syrup-like, and waxy substances at room temperature. Here, room temperature in this specification refers to 25°C.

[0014] 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. Embodiments that combine any combination of the information described herein are also included.

[0015] [Resin composition] The resin composition of this embodiment is (A) Thermosetting resin and (B) Titanium-based inorganic filler, (C) Siloxane compound having a reactive group, This is a resin composition comprising the following:

[0016] In the following explanation, (A) thermosetting resin may be referred to as "component (A)". Furthermore, (B) titanium-based inorganic filler is sometimes referred to as "component (B)". Furthermore, siloxane compounds having a (C) reactive group are sometimes referred to as "(C) component".

[0017] The reason why the resin composition of this embodiment exhibits low thermal expansion while suppressing changes in relative permittivity (Dk) is presumed to be as follows. The resin composition of this embodiment is comprised of (B) a titanium-based inorganic filler having a high dielectric constant (Dk), and (C) a siloxane compound having a reactive group. The siloxane compound having the (C) reactive group has the effect of reducing the elastic modulus of the resin composition. Furthermore, it is thought that the thermal expansion and contraction of the resin composition, whose elastic modulus has been reduced by the incorporation of the siloxane compound having the (C) reactive group, will be more easily constrained by the constituent members which have a lower coefficient of thermal expansion than the resin composition. Therefore, it is considered that the resin composition of this embodiment has an effective reduction in coefficient of thermal expansion without the dielectric constant (Dk) deviating significantly from the design value. The following describes each component that may be contained in the resin composition of this embodiment.

[0018] <(A) Thermosetting resin> (A) Examples of thermosetting resins include epoxy resins, phenolic resins, maleimide resins, cyanate resins, isocyanate resins, benzoxazine resins, oxetane resins, amino resins, unsaturated polyester resins, allyl resins, dicyclopentadiene resins, silicone resins, triazine resins, melamine resins, and the like. (A) Thermosetting resins may be used individually or in combination of two or more types. Among these, (A) as the thermosetting resin, maleimide resin is preferred from the viewpoint of heat resistance, low thermal expansion, and (B) being less susceptible to unintended curing acceleration effects by titanium-based inorganic fillers and having excellent moldability for circuit embedding, and more preferably one or more selected from the group consisting of maleimide compounds having one or more N-substituted maleimide groups and their derivatives. In the following explanation, "one or more selected from the group consisting of maleimide compounds having one or more N-substituted maleimide groups and their derivatives" may be referred to as "maleimide resins." Furthermore, in the following explanation, maleimide compounds having one or more N-substituted maleimide groups may be referred to as "maleimide compounds (AX)" or "(AX) components." Furthermore, derivatives of maleimide compounds having one or more N-substituted maleimide groups may be referred to as "maleimide compound derivatives (AY)" or "(AY) components."

[0019] (Maleimide compound (AX)) The maleimide compound (AX) is not particularly limited as long as it is a maleimide compound having one or more N-substituted maleimide groups. As for the maleimide compound (AX), a maleimide compound (A1) having two or more N-substituted maleimide groups [hereinafter, it may be referred to as "maleimide compound (A1)" or "component (A1)"] is preferred from the viewpoint of dielectric properties, conductive adhesion and heat resistance, an aromatic maleimide compound having two or more N-substituted maleimide groups is more preferred, and an aromatic bismaleimide compound having two N-substituted maleimide groups is even more preferred. In this specification, "aromatic maleimide compound" means a compound having an N-substituted maleimide group directly bonded to an aromatic ring, and "aromatic bismaleimide compound" means a compound having two N-substituted maleimide groups directly bonded to an aromatic ring.

[0020] [Maleimide compound (A1)] As the maleimide compound (A1), a maleimide compound represented by the following general formula (A1-1) is preferred.

[0021] [ka] (In the formula, X a11 (This is a divalent organic group.)

[0022] X in the above general formula (A1-1) a11 It is a divalent organic group. X in the above general formula (A1-1) a11Examples of the divalent organic group represented by [the relevant part] include a divalent group represented by the following general formula (A1-2), a divalent group represented by the following general formula (A1-3), a divalent group represented by the following general formula (A1-4), a divalent group represented by the following general formula (A1-5), a divalent group represented by the following general formula (A1-6), and the like.

[0023] [Chemical formula] (In the formula, R a11 is an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. n a11 is an integer of 0 to 4. * represents a bonding site.)

[0024] Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R a11 in the above general formula (A1-2) include alkyl groups having 1 to 5 carbon atoms such as 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; alkenyl groups having 2 to 5 carbon atoms, alkynyl groups having 2 to 5 carbon atoms, and the like. The aliphatic hydrocarbon group having 1 to 5 carbon atoms may be either linear or branched. Among them, the aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferred, the alkyl group having 1 to 3 carbon atoms is more preferred, and the methyl group is even more preferred. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like. n a11 in the above general formula (A1-2) is an integer of 0 to 4, and from the viewpoint of easy availability, it is preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0. n a11 When n a11 is an integer of 2 or more, the plurality of R

[0025] [Chemical formula] (In the formula, R a12 and Ra13 Each of these is independently an aliphatic hydrocarbon group or halogen atom having 1 to 5 carbon atoms. a12 n 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 (A1-3-1). a12 and n a13 Each of these is an independent integer between 0 and 4. * represents a connection point.

[0026] In the above general formula (A1-3), R a12 and R a13 Examples of C1-C5 aliphatic hydrocarbon groups represented by include C1-C5 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, and n-pentyl groups; C2-C5 alkenyl groups; and C2-C5 alkynyl groups. The C1-C5 aliphatic hydrocarbon group may be linear or branched. The C1-C5 aliphatic hydrocarbon group is preferably a C1-C3 aliphatic hydrocarbon group, more preferably a C1-C3 alkyl group, and even more preferably a methyl or ethyl group. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms.

[0027] X in the above general formula (A1-3) a12 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. Among the alkylene groups having 1 to 5 carbon atoms, 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.

[0028] X in the above general formula (A1-3) a12Examples of alkylidene groups having 2 to 5 carbon atoms include ethylidene, propyridene, isopropylidene, butyridene, isobutylidene, pentyridene, and isopentylidene. Among these, alkylidene groups having 2 to 4 carbon atoms are preferred, alkylidene groups having 2 or 3 carbon atoms are more preferred, and isopropylidene groups are even more preferred.

[0029] n in the above general formula (A1-3) a12 and n a13 Each of these is an integer between 0 and 4, independently of the others. n a12 or n a13 If is an integer greater than or equal to 2, then multiple R a12 Each or multiple R a13 They may be the same or they may be different.

[0030] X in the above general formula (A1-3) a12 The divalent group represented by the general formula (A1-3-1) is as follows:

[0031] [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. a13 This 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, or a single bond. a14 and n a15 Each of these is an independent integer between 0 and 4. * represents a connection point.

[0032] In the above general formula (A1-3-1), R a14 and R a15Examples of C1-C5 aliphatic hydrocarbon groups represented by include C1-C5 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, and n-pentyl groups; C2-C5 alkenyl groups; and C2-C5 alkynyl groups. The C1-C5 aliphatic hydrocarbon group may be linear or branched. The C1-C5 aliphatic hydrocarbon group is preferably a C1-C3 aliphatic hydrocarbon group, more preferably a C1-C3 alkyl group, and even more preferably a methyl group. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms.

[0033] X in the above general formula (A1-3-1) a13 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. Among the alkylene groups having 1 to 5 carbon atoms, 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.

[0034] X in the above general formula (A1-3-1) a13 Examples of alkylidene groups having 2 to 5 carbon atoms include ethylidene, propyridene, isopropylidene, butyridene, isobutylidene, pentyridene, and isopentylidene. Among these, alkylidene groups having 2 to 4 carbon atoms are preferred, alkylidene groups having 2 or 3 carbon atoms are more preferred, and isopropylidene groups are even more preferred.

[0035] X in the above general formula (A1-3-1) a13 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.

[0036] n in the above general formula (A1-3-1) a14 and n a15Each of these is an integer between 0 and 4, and from the viewpoint of availability, each is preferably an integer between 0 and 2, more preferably 0 or 1, and even more preferably 0. n a14 or n a15 If is an integer greater than or equal to 2, then multiple R a14 Each or multiple R a15 They may be the same or they may be different.

[0037] X in the above general formula (A1-3) a12 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 (A1-3-1) are preferred, alkylene groups having 1 to 5 carbon atoms are more preferred, and methylene groups are even more preferred.

[0038] [ka] (In the formula, n a16 (This is an integer between 0 and 10. * represents a connection point.)

[0039] n in the above general formula (A1-4) a16 From the viewpoint of availability, the integer 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.

[0040] [ka] (In the formula, n a17 (The numbers are 0-5. * represents a connection site.)

[0041] [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. a18 (This is an integer between 1 and 8. * represents a connection point.)

[0042] In the above general formula (A1-6), R a16 and R a17 Examples of C1-C5 aliphatic hydrocarbon groups represented by include C1-C5 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, and n-pentyl groups; C2-C5 alkenyl groups; and C2-C5 alkynyl groups. The C1-C5 aliphatic hydrocarbon group may be linear or branched. n in the above general formula (A1-6) a18 n is an integer between 1 and 8, preferably between 1 and 5, more preferably between 1 and 3, and even more preferably 1. a18 If is an integer greater than or equal to 2, then multiple R a16 Each or multiple R a17 They may be the same or they may be different.

[0043] Examples of maleimide compounds (A1) include aromatic bismaleimide compounds, aromatic polymaleimide compounds, and aliphatic maleimide compounds. Specific examples of maleimide compounds (A1) include N,N'-ethylenebismaleimide, N,N'-hexamethylenebismaleimide, N,N'-(1,3-phenylene)bismaleimide, N,N'-[1,3-(2-methylphenylene)]bismaleimide, N,N'-[1,3-(4-methylphenylene)]bismaleimide, N,N'-(1,4-phenylene)bismaleimide, bis(4-maleimidophenyl)methane, bis(3-methyl-4-maleimidophenyl)methane, and 3,3'-dimethyl-5,5'-diethyl -4,4'-diphenylmethanebismaleimide, bis(4-maleimidophenyl) ether, bis(4-maleimidophenyl) sulfone, bis(4-maleimidophenyl) sulfide, bis(4-maleimidophenyl) ketone, bis(4-maleimidocyclohexyl)methane, 1,4-bis(4-maleimidophenyl)cyclohexane, 1,4-bis(maleimidomethyl)cyclohexane, 1,4-bis(maleimidomethyl)benzene, 1,3-bis(4-maleimidophenoxy)benzene, 1,3-bis(3- (maleimidophenoxy)benzene, bis[4-(3-maleimidophenoxy)phenyl]methane, bis[4-(4-maleimidophenoxy)phenyl]methane, 1,1-bis[4-(3-maleimidophenoxy)phenyl]ethane, 1,1-bis[4-(4-maleimidophenoxy)phenyl]ethane, 1,2-bis[4-(3-maleimidophenoxy)phenyl]ethane, 1,2-bis[4-(4-maleimidophenoxy)phenyl]ethane, 2,2-bis[4-(3-maleimidophenoxy)phenyl]propane , 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, 2,2-bis[4-(3-maleimidophenoxy)phenyl]butane, 2,2-bis[4-(4-maleimidophenoxy)phenyl]butane, 2,2-bis[4-(3-maleimidophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[4-(4-maleimidophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 4,4-bis(3-maleimidophenoxy)biphenyl, 4,4-Bis(4-maleimidophenoxy)biphenyl, bis[4-(3-maleimidophenoxy)phenyl]ketone, bis[4-(4-maleimidophenoxy)phenyl]ketone, bis(4-maleimidophenoxy)disulfide, bis[4-(3-maleimidophenoxy)phenyl]sulfide, bis[4-(4-maleimidophenoxy)phenyl]sulfide, bis[4-(3-maleimidophenoxy)phenyl]sulfoxide, bis[4-(4-maleimidophenoxy)phenyl]sulfoxide, bis[4-(3-maleimidophenoxy)phenyl]sulfone, bis[4-(4-maleimidophenoxy)phenyl]sulfone, bis[4-(3-maleimidophenoxy)phenyl]ether, bis[4-(4-maleimidophenoxy)phenyl]ether, 1,4-bis[4-(4-maleimidophenoxy)-α,α Examples include -dimethylbenzylbenzene, 1,3-bis[4-(4-maleimidophenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(3-maleimidophenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(3-maleimidophenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(4-maleimidophenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-maleimidophenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(3-maleimidophenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(3-maleimidophenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, polyphenylmethanemaleimide, etc. Among these, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane is preferred.

[0044] (Maleimide compounds are derivatives (AY)) As the maleimide compound derivative (AY), an aminomaleimide compound having structural units derived from the above-mentioned maleimide compound (AX) and structural units derived from a diamine compound [hereinafter, this may be referred to as "aminomaleimide compound (A2)" or "component (A2)"] is preferred.

[0045] [Aminomaleimide compound (A2)] The aminomaleimide compound (A2) has structural units derived from the maleimide compound (AX) and structural units derived from the diamine compound [hereinafter, it may be referred to as "diamine compound (a)" or "component (a)"].

[0046] In this embodiment, the aminomaleimide compound (A2) is classified as a (A) thermosetting resin, and the diamine compound (a) obtained by reacting with the maleimide compound (AX) and the diamine compound (a) intended to be reacted with the maleimide compound (AX) are also classified as (A) thermosetting resins. However, the (C) component described later is excluded from the diamine compound (a). In other words, component (C), described later, is a diamine compound, and component (C) reacted with maleimide compound (AX), as well as component (C) intended to be reacted with maleimide compound (AX), are not classified as (A) thermosetting resins.

[0047] 《Structural units derived from maleimide compounds (AX)》 Examples of structural units derived from maleimide compounds (AX) include structural units formed when at least one N-substituted maleimide group of the maleimide compound (AX) undergoes a Michael addition reaction with an amino group of the diamine compound. The structural units derived from the maleimide compound (AX) contained in the aminomaleimide compound (A2) may be a single type or two or more types.

[0048] The content of structural units derived from maleimide compound (AX) in aminomaleimide compound (A2) is not particularly limited, but is preferably 5 to 95% by mass, more preferably 30 to 93% by mass, and even more preferably 60 to 90% by mass. When the content of structural units derived from maleimide compound (AX) in aminomaleimide compound (A2) is within the above range, dielectric properties and film handling properties tend to be better.

[0049] 《Structural unit derived from diamine compound (a)》 Examples of structural units derived from diamine compound (a) include structural units formed by a Michael addition reaction between one or both of the two amino groups of diamine compound (a) and an N-substituted maleimide group of maleimide compound (AX). The structural units derived from the diamine compound (a) contained in the aminomaleimide compound (A2) may be single or two or more.

[0050] The amino group in diamine compound (a) is preferably a primary amino group. Examples of structural units derived from diamine compound (a) having two primary amino groups include the group represented by the following general formula (a-1) and the group represented by the following general formula (a-2).

[0051] [ka] (In the formula, X a21 (where * represents a divalent organic group, and * represents a bonding site.)

[0052] X in the above general formula (a-1) and the above general formula (a-2) a21 This is a divalent organic group, corresponding to the divalent group obtained by removing two primary amino groups from diamine compound (a).

[0053] X in the above general formula (a-1) and the above general formula (a-2) a21 It is preferable that the group is a divalent group represented by the following general formula (a-3).

[0054] [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. a22n is a divalent group represented by the following general formula (a-3-1) or (a-3-2). a21 and n a22 Each of these is an independent integer between 0 and 4. * represents a connection point.

[0055] [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. a23 This is an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 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. a23 and n a24 Each of these is an independent integer between 0 and 4. * represents a connection point.

[0056] [ka] (In the formula, R a25 X is an aliphatic hydrocarbon group or halogen atom having 1 to 5 carbon atoms. a24 and X a25 Each of these is 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. a25 (This is an integer between 0 and 4. * represents a connection site.)

[0057] In the above general formula (a-3), the above general formula (a-3-1), and the above general formula (a-3-2), R a21 , R a22 , R a23 , R a24 and R a25Examples of C1-C5 aliphatic hydrocarbon groups represented by include C1-C5 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, and n-pentyl groups; C2-C5 alkenyl groups; and C2-C5 alkynyl groups. The C1-C5 aliphatic hydrocarbon group may be linear or branched. The C1-C5 aliphatic hydrocarbon group is preferably a C1-C3 aliphatic hydrocarbon group, more preferably a C1-C3 alkyl group, and even more preferably a methyl or ethyl group. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms.

[0058] X in the above general formula (a-3) a22 , X in the above general formula (a-3-1) a23 Furthermore, X in the above general formula (a-3-2) a24 and X a25 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. Among the alkylene groups having 1 to 5 carbon atoms, 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.

[0059] X in the above general formula (a-3) a22 , X in the above general formula (a-3-1) a23 , and X in the above general formula (a-3-2) a24 and X a25 Examples of alkylidene groups having 2 to 5 carbon atoms include ethylidene, propyridene, isopropylidene, butyridene, isobutylidene, pentyridene, and isopentyridene. Among the alkylidene groups having 2 to 5 carbon atoms, alkylidene groups having 2 to 4 carbon atoms are preferred, alkylidene groups having 2 or 3 carbon atoms are more preferred, and isopropylidene groups are even more preferred.

[0060] n in the above general formula (a-3) a21 and na22 is, independently of each other, an integer from 0 to 4, and from the viewpoint of availability, each is preferably an integer from 0 to 3, more preferably an integer from 0 to 2, and even more preferably 0 or 2. n a21 or n a22 When is an integer of 2 or more, a plurality of R a21 each other or a plurality of R a22 each other may be the same or different from each other.

[0061] n in the general formula (a-3-1) above a23 and n a24 are, independently of each other, an integer from 0 to 4, and from the viewpoint of availability, each is preferably an integer from 0 to 2, more preferably 0 or 1, and even more preferably 0. n a23 or n a24 When is an integer of 2 or more, a plurality of R a23 each other or a plurality of R a24 each other may be the same or different from each other.

[0062] n in the general formula (a-3-2) above a25 is an integer from 0 to 4, and from the viewpoint of availability, is preferably an integer from 0 to 2, more preferably 0 or 1, and even more preferably 0. n a25 When is an integer of 2 or more, a plurality of R a25 each other may be the same or different from each other.

[0063] The content of the structural unit derived from the diamine compound (a) in the aminomaleimide compound (A2) is not particularly limited, but is preferably 5 to 95% by mass, more preferably 7 to 70% by mass, and even more preferably 10 to 40% by mass. When the content of the structural unit derived from the diamine compound (a) in the aminomaleimide compound (A2) is within the above range, the dielectric properties, heat resistance and glass transition temperature tend to be better.

[0064] Examples of diamine compounds (a) include 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ketone, 4,4'-diaminobiphenyl, and 3,3' -dimethyl-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 -Bis(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, Examples include 3-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.

[0065] Among these, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 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 as diamine compound (a) from the viewpoint of excellent solubility in organic solvents, reactivity, and heat resistance.

[0066] In the aminomaleimide compound (A2), the equivalent ratio (Ta2) of the total equivalent of groups derived from the -NH2 group of the diamine compound (a) (including -NH2) to the total equivalent of groups derived from the N-substituted maleimide group of the maleimide compound (AX) (Ta1) is not particularly limited, but from the viewpoint of dielectric properties, heat resistance and glass transition temperature, it is preferably 0.05 to 10, more preferably 0.5 to 7, and even more preferably 1 to 5. The groups derived from the -NH2 group of the diamine compound (a) above include the -NH2 itself. Also, the groups derived from the N-substituted maleimide group of the maleimide compound (AX) above include the N-substituted maleimide group itself.

[0067] The weight-average molecular weight (Mw) of the aminomaleimide compound (A2) is not particularly limited, but is preferably 400 to 10,000, more preferably 500 to 6,000, and even more preferably 1,000 to 6,000. The weight-average molecular weight (Mw) of the aminomaleimide compound (A2) can be measured by the method described in the examples.

[0068] (Method for producing aminomaleimide compound (A2)) The aminomaleimide compound (A2) can be produced, for example, by reacting the maleimide compound (AX) with the diamine compound (a) in an organic solvent. By reacting maleimide compound (AX) with diamine compound (a), an aminomaleimide compound (A2) is obtained through a Michael addition reaction between maleimide compound (AX) and diamine compound (a).

[0069] When reacting the maleimide compound (AX) with the diamine compound (a), 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. These may be used individually or in combination of two or more. The amount of reaction catalyst is not particularly limited, but from the viewpoint of reaction rate and reaction uniformity, it is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, and even more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the total amount of maleimide compound (AX) and diamine compound (a).

[0070] The reaction temperature for the Michael addition reaction is preferably 50 to 160°C, more preferably 60 to 150°C, and even more preferably 70 to 140°C, from the viewpoint of workability such as reaction rate and suppression of product gelation during the reaction. The reaction time for the Michael addition reaction is preferably 0.5 to 10 hours, more preferably 1 to 8 hours, and even more preferably 2 to 6 hours, from the viewpoint of productivity and ensuring the reaction proceeds sufficiently. However, these reaction conditions can be adjusted as appropriate depending on the type of raw materials used, and are not particularly limited.

[0071] In the Michael addition reaction, the solid content concentration and viscosity of the reaction solution may be adjusted by adding or concentrating an organic solvent. The solid content concentration of the reaction solution 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 of the product during the reaction tends to be further suppressed.

[0072] In the resin composition of this embodiment, the amount of (A) thermosetting resin is not particularly limited, but is preferably 5 to 98% by mass, more preferably 10 to 95% by mass, and even more preferably 20 to 92% by mass, relative to the total amount (100% by mass) of the resin components in the resin composition of this embodiment. (A) When the amount of thermosetting resin blended is above the lower limit, the heat resistance, moldability, processability, and conductor adhesion tend to be better. Also, (A) when the amount of thermosetting resin blended is below the upper limit, the dielectric properties tend to be better.

[0073] (A) The amount of the maleimide resin blended in the thermosetting resin is not particularly limited, but is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, and even more preferably 95 to 100% by mass, relative to (A) thermosetting resin (100% by mass). When the amount of maleimide resin blended is above the lower limit, heat resistance, moldability, processability, and conductor adhesion tend to be better. Conversely, when the amount of maleimide resin blended is below the upper limit, dielectric properties tend to be better.

[0074] Herein, in this specification, "resin component" means resin and compounds that form resin through a curing reaction. For example, in the resin composition of this embodiment, (A) a thermosetting resin and (C) a siloxane compound having a reactive group correspond to the resin components. If the resin composition of this embodiment contains, as an optional component, a resin or a compound that forms a resin by a curing reaction in addition to the above-mentioned components, these optional components are also included in the resin component, and the curing accelerator described later is also included in the resin component. On the other hand, inorganic fillers and flame retardants shall not be included in the resin components.

[0075] In the resin composition of this embodiment, the amount of resin component is not particularly limited, but is preferably 10 to 80% by mass, more preferably 30 to 75% by mass, and even more preferably 35 to 70% by mass, relative to the total solid content of the resin composition. When the amount of resin component is above the lower limit, heat resistance, moldability, processability, and conductor adhesion tend to be better. Conversely, when the amount of resin component is below the upper limit, dielectric properties tend to be better.

[0076] <(B) Titanium-based inorganic filler> The resin composition of this embodiment contains (B) a titanium-based inorganic filler. (B) Titanium-based inorganic fillers may be used individually or in combination of two or more types.

[0077] (B) Examples of titanium-based inorganic fillers include titanium dioxide and titanates. Among these, titanates are preferred from the viewpoint of easily increasing the dielectric constant (Dk) of the cured resin composition. Examples of titanates include alkali metal titanates and alkaline earth metal titanates. Among these, from the viewpoint of easily increasing the dielectric constant (Dk) of the cured resin composition, one or more selected from the group consisting of barium titanate, potassium titanate, calcium titanate, strontium titanate, lead titanate, and aluminum titanate are preferred, with calcium titanate and strontium titanate being more preferred.

[0078] (B) Average particle size of titanium-based inorganic filler (D 50The particle size is not particularly limited, but is preferably 0.1 to 20 μm, more preferably 0.5 to 15 μm, and even more preferably 0.7 to 10 μm. (B) Average particle size of titanium-based inorganic filler (D 50 If (B) is above the lower limit, the specific surface area of ​​the titanium-based inorganic filler becomes smaller, and the unintended acceleration of the curing reaction of the thermosetting resin by the solid surface of the titanium-based inorganic filler tends to be suppressed. Also, the average particle size (D) of the titanium-based inorganic filler 50 When the above upper limit is below the specified value, the homogeneity of the cured resin composition tends to be better. (B) Average particle size of titanium-based inorganic filler (D 50 ) can be measured by the method described in the examples.

[0079] (B) The dielectric constant (Dk) of the titanium-based inorganic filler at 10 GHz is not particularly limited, but is preferably 10 to 3,000, more preferably 13 to 2,500, and even more preferably 15 to 2,000. (B) When the relative permittivity (Dk) of the titanium-based inorganic filler at 10 GHz is above the lower limit, it tends to be easier to increase the relative permittivity (Dk) of the cured resin composition. Also, when the relative permittivity (Dk) of the titanium-based inorganic filler at 10 GHz is below the upper limit, it tends to be easier to maintain a good balance between availability and other physical properties. (B) The relative permittivity (Dk) of the titanium-based inorganic filler at 10 GHz can be measured by the method described in the examples.

[0080] The amount of (B) titanium-based inorganic filler in the resin composition of this embodiment is not particularly limited, but is preferably 20 to 80% by mass, more preferably 30 to 75% by mass, and even more preferably 40 to 70% by mass, relative to the total solid content of the resin composition. (B) When the amount of titanium-based inorganic filler is above the lower limit, the dielectric constant (Dk) of the cured resin composition tends to be higher. Also, when the amount of titanium-based inorganic filler is below the upper limit, the moldability tends to be better.

[0081] <(C) Siloxane compounds having reactive groups> (C) The siloxane compound having a reactive group is not particularly limited as long as it has a reactive group in its molecule and has at least one siloxane bond. (C) Siloxane compounds having a reactive group may be used individually or in combination of two or more.

[0082] (C) Siloxane compounds having a reactive group are preferably those containing a structural unit represented by the following general formula (C-1), and polysiloxane compounds containing a structure represented by the following general formula (C-2) are more preferably.

[0083] [ka] (In the formula, R c1 and R c2 Each of these is independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms, a phenyl group, or a substituted phenyl group. (* indicates a bonding site.)

[0084] [ka] (In the formula, R c1 and R c2 This is the same as the one in the general formula (C-1) above, and R c3 and R c4 Each of these is independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms, a phenyl group, or a substituted phenyl group. c1 and X c2 Each of these is independently a divalent organic group, and n c1 (This is an integer between 2 and 100. * represents the site where the reactive group is attached.)

[0085] In the above general formulas (C-1) and (C-2), R c1 ~R c4Examples of C1-C5 aliphatic hydrocarbon groups represented by (C1) include C1-C5 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, and n-pentyl groups; C2-C5 alkenyl groups; and C2-C5 alkynyl groups. The C1-C5 aliphatic hydrocarbon group may be linear or branched. C1-C3 aliphatic hydrocarbon groups are preferred, C1-C3 alkyl groups are more preferred, and methyl groups are even more preferred. In other words, the structural unit represented by the general formula (C1) is preferably a dimethylsiloxane unit. R c1 ~R c4 Examples of substituents on the phenyl group in the substituted phenyl group represented by include the aliphatic hydrocarbon groups having 1 to 5 carbon atoms as described above.

[0086] X c1 and X c2 Examples of divalent organic groups represented by include alkylene groups, alkenylene groups, alkynylene groups, arylene groups, -O- groups, or divalent linking groups formed by combinations of these groups. Examples of the alkylene group mentioned above include methylene, ethylene, and propylene groups. The number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 2 to 7, and even more preferably 2 to 5. Examples of the above-mentioned alkenylene group include alkenylene groups having 2 to 10 carbon atoms. Examples of the alkynylene group mentioned above include alkynylene groups having 2 to 10 carbon atoms. Examples of the above-mentioned arylene groups include phenylene groups, naphthylene groups, and other arylene groups having 6 to 20 carbon atoms. Among these, X c1 and X c2 Of these, alkylene groups and arylene groups are preferred, with alkylene groups being more preferred.

[0087] n c1n is an integer between 2 and 100, preferably between 2 and 50, more preferably between 3 and 40, and even more preferably between 5 and 30. c1 If is an integer greater than or equal to 2, then multiple R c1 Each or multiple R c2 They may be the same or they may be different.

[0088] (C) The siloxane compound having a reactive group may be a linear polysiloxane compound or a branched polysiloxane compound, but it is preferably a linear polysiloxane compound.

[0089] (C) Examples of reactive groups in a siloxane compound having a reactive group include epoxy groups, amino groups, vinyl groups, hydroxyl groups, methacrylic groups, mercapto groups, carboxyl groups, alkoxy groups, and silanol groups. (C) A siloxane compound having a reactive group may contain one or more of the above reactive groups. Among these, amino groups and vinyl groups are preferred as reactive groups, with amino groups being more preferred. Of the amino groups, primary amino groups and secondary amino groups are preferred, with primary amino groups being more preferred. In other words, (C) the siloxane compound having a reactive group is preferably an amino-modified siloxane compound having a primary amino group.

[0090] (C) When the siloxane compound having a reactive group is a polysiloxane compound, the reactive group may be introduced into the side chain of the polysiloxane compound, but it is preferable that it be introduced into the terminal of the polysiloxane compound. Furthermore, when the reactive group is at the terminal, the reactive group may be introduced into one terminal, but it is preferable that it is introduced into both terminals. In other words, (C) the siloxane compound having a reactive group is preferably an amino-modified siloxane compound having primary amino groups at both terminals.

[0091] (C) The number of reactive groups in a siloxane compound having reactive groups is not particularly limited, but is preferably 1 to 5, more preferably 1 to 3, and even more preferably 2.

[0092] (C) The reactive group equivalent of the siloxane compound having a reactive group is not particularly limited, but is preferably 200 to 5,000 g / mol, more preferably 400 to 4,000 g / mol, and even more preferably 500 to 3,000 g / mol.

[0093] The amount of the siloxane compound having a (C) reactive group in the resin composition of this embodiment is not particularly limited, but is preferably 1 to 50 parts by mass, more preferably 3 to 30 parts by mass, and even more preferably 5 to 15 parts by mass, based on 100 parts by mass of the total amount of resin components in the resin composition of this embodiment. (C) When the amount of siloxane compound having a reactive group is above the lower limit, it tends to be easier to reduce the thermal expansion coefficient of the cured resin composition. Also, when the amount of siloxane compound having a reactive group is below the upper limit, it tends to be easier to reduce the variation in the dielectric constant (Dk) of the cured resin composition due to the addition of siloxane compound having a reactive group.

[0094] The resin composition of this embodiment may be obtained by reacting (C) a siloxane compound having a reactive group with (A) a thermosetting resin and then blending them together. (C) A preferred method of reacting a siloxane compound having a reactive group with a thermosetting resin (A) is to react an amino-modified siloxane compound as component (C) with a maleimide-based resin as the thermosetting resin (A). A more preferred method is to react an amino-modified siloxane compound having primary amino groups at both ends as component (C) with a maleimide-based resin as the thermosetting resin (A). An even more preferred method is to react an amino-modified siloxane compound having primary amino groups at both ends as component (C) with a maleimide compound (AX) as the thermosetting resin (A). A particularly preferred method is to react an amino-modified siloxane compound having primary amino groups at both ends as component (C) with a diamine compound (a) (excluding the amino-modified siloxane compound) together with a maleimide compound (AX) as the thermosetting resin (A).

[0095] In this specification, an aminomaleimide compound obtained by reacting an amino-modified siloxane compound having primary amino groups at both ends as component (C) with a diamine compound (a) (excluding amino-modified siloxane compounds) and a maleimide compound (AX), having a structural unit (i) derived from the maleimide compound (AX), a structural unit (ii) derived from the amino-modified siloxane compound having primary amino groups at both ends, and a structural unit (iii) derived from the diamine compound (a) (excluding amino-modified siloxane compounds), may be referred to as an "aminomaleimide compound (AC)".

[0096] If the resin composition of this embodiment contains an aminomaleimide compound (AC), then the resin composition of this embodiment can be said to be a mixture of (A) one or more selected from the group consisting of maleimide compounds and derivatives thereof having one or more N-substituted maleimide groups as thermosetting resins, and (C) a siloxane compound having a reactive group. In this case, the resin composition of this embodiment may, in addition to the aminomaleimide compound (AC), further contain one or more selected from the group consisting of components (A) and (C), but may not contain them.

[0097] In the aminomaleimide compound (AC), the content of structural unit (i) is not particularly limited, but is preferably 40 to 90% by mass, more preferably 50 to 85% by mass, and even more preferably 60 to 80% by mass, relative to the total amount of all structural units. When the content of structural unit (i) is above the lower limit, heat resistance, moldability, processability, and conductor adhesion tend to be better. Conversely, when the content of structural unit (i) is below the upper limit, dielectric properties tend to be better.

[0098] In the aminomaleimide compound (AC), the content of structural unit (ii) is not particularly limited, but is preferably 1 to 40% by mass, more preferably 5 to 30% by mass, and even more preferably 10 to 20% by mass, relative to the total amount of all structural units. When the content of structural unit (ii) is within the above range, dielectric properties, heat resistance, and glass transition temperature tend to be better.

[0099] In the aminomaleimide compound (AC), the content of structural unit (iii) is not particularly limited, but is preferably 0.5 to 35% by mass, more preferably 2 to 25% by mass, and even more preferably 5 to 15% by mass, relative to the total amount of all structural units. When the content of structural unit (iii) is above the lower limit, it tends to reduce the thermal expansion coefficient of the cured resin composition. Also, when the content of structural unit (iii) is below the upper limit, it tends to reduce the variation in the dielectric constant (Dk) of the cured resin composition due to the addition of a siloxane compound having a reactive group (C).

[0100] In the aminomaleimide compound (AC), the ratio of the total number of moles of structural unit (ii) and structural unit (iii) to the number of moles of structural unit (i) is not particularly limited, but from the viewpoint of dielectric properties, heat resistance and glass transition temperature, it is preferably 0.05 to 10, more preferably 0.5 to 7, and even more preferably 1 to 5.

[0101] The description of the method for producing aminomaleimide compound (AC) is the same as the description of the method for producing aminomaleimide compound (A2).

[0102] The amount of aminomaleimide compound (AC) in the resin composition of this embodiment is not particularly limited, but is preferably 10 to 80% by mass, more preferably 20 to 60% by mass, and even more preferably 30 to 50% by mass, based on the total solid content of the resin composition. When the amount of aminomaleimide compound (AC) is above the lower limit, the balance of heat resistance, moldability, processability, conductor adhesion, and low thermal expansion tends to be better. Conversely, when the amount of aminomaleimide compound (AC) is below the upper limit, the dielectric constant (Dk) of the cured product tends to be higher.

[0103] <(D) Curing accelerator> From the viewpoint of promoting the curing reaction of the resin composition, it is preferable that the resin composition of this embodiment further contains (D) a curing accelerator. (D) The curing accelerator may be used alone or in combination of two or more types.

[0104] (D) Examples of curing accelerators include acidic catalysts such as p-toluenesulfonic acid; amine compounds such as triethylamine, pyridine, tributylamine, and dicyandiamide; imidazole compounds such as methylimidazole, phenylimidazole, and 1-cyanoethyl-2-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, amine compounds and imidazole compounds are preferred from the viewpoint of curing acceleration effect and storage stability, and dicyandiamide and 1-cyanoethyl-2-phenylimidazole are more preferred.

[0105] When (D) a curing accelerator is added to the resin composition of this embodiment, the amount added is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and even more preferably 0.5 to 2 parts by mass, per 100 parts by mass of (A) thermosetting resin. (D) When the amount of curing accelerator added is above the lower limit, a sufficient curing acceleration effect tends to be easily obtained. Also, when the amount of curing accelerator added is below the upper limit, storage stability tends to be better.

[0106] <Other ingredients> The resin composition of this embodiment may contain, or may not contain, other components in addition to the above-mentioned components, as needed. Other components include, for example, (A) resins other than thermosetting resins, (B) inorganic fillers other than the components, flame retardants, organic solvents, and other additives. Each of these may be used individually or in combination of two or more types.

[0107] (A) Examples of resins other than thermosetting resins include thermoplastic resins. Examples of thermoplastic resins include polyphenylene ether resins; styrene-based thermoplastic elastomers, olefin-based thermoplastic elastomers, urethane-based thermoplastic elastomers, polyester-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, acrylic-based thermoplastic elastomers, silicone-based thermoplastic elastomers, and their derivatives.

[0108] Examples of inorganic fillers other than component (B) include silica, alumina, mica, beryllium, aluminum carbonate, magnesium hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay, talc, aluminum borate, silicon carbide, etc.

[0109] Examples of flame retardants include phosphorus-based flame retardants, metal hydrates, and halogen-based flame retardants. Among these, phosphorus-based flame retardants and metal hydrates are preferred from an environmental perspective. While the phosphorus-based flame retardant may be an inorganic phosphorus-based flame retardant, an organic phosphorus-based flame retardant is preferred from the viewpoint of dielectric properties, adhesion to conductors, heat resistance, glass transition temperature, low thermal expansion, and flame retardancy. 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, cyclic organophosphorus compounds, and phosphine oxide compounds. Examples of metal salts of disubstituted phosphinic acid include lithium salts, sodium salts, potassium salts, calcium salts, magnesium salts, aluminum salts, titanium salts, and zinc salts.

[0110] Examples of organic solvents include acetone, methyl ethyl ketone, toluene, xylene, cyclohexanone, 4-methyl-2-pentanone, ethyl acetate, ethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, N,N-dimethylformamide, and N,N-dimethylacetamide.

[0111] Other additives include, for example, UV absorbers such as benzotriazoles; antioxidants such as hindered phenol antioxidants and styrene-phenol antioxidants; photopolymerization initiators such as benzophenones, benzyl ketals, and thioxanthones; fluorescent whitening agents such as stilbene derivatives; adhesion enhancers such as urea compounds and silane coupling agents; and crosslinking agents such as cyanamide crosslinking agents.

[0112] The content of other components is not particularly limited and may be used as needed, within a range that does not hinder the effects of this embodiment.

[0113] <Method for producing resin compositions> The resin composition of this embodiment can be manufactured by mixing the above-mentioned components. When mixing the components, each component may be dissolved or dispersed while being stirred. Furthermore, the order in which the raw materials are mixed, the mixing temperature, the mixing time, and other conditions are not particularly limited and can be set arbitrarily according to the type of raw materials, etc.

[0114] <Permittivity (Dk) of the cured material> The dielectric constant (Dk) of the cured resin composition of this embodiment at 20 GHz is not particularly limited, but is preferably 2 to 50, more preferably 4 to 40, and even more preferably 5 to 35. If the relative permittivity (Dk) of the cured material at 20 GHz is above the lower limit mentioned above, it tends to be easier to miniaturize the antenna module. Conversely, if the relative permittivity (Dk) of the cured material at 20 GHz is below the upper limit mentioned above, it tends to be easier to maintain a good balance with other physical properties. The dielectric constant (Dk) of the cured resin composition of this embodiment at 20 GHz can be measured by the method described in the examples.

[0115] <Thermal expansion coefficient of cured material> The thermal expansion coefficient of the cured prepreg produced by the method described in the Examples using the resin composition of this embodiment is not particularly limited, but from the viewpoint of easily suppressing the occurrence of warping, it is preferably 30 ppm / °C or less, more preferably 25 ppm / °C or less, and even more preferably 20 ppm / °C or less. There are no particular restrictions on the lower limit of the thermal expansion coefficient of the cured prepreg described above. However, from the viewpoint of maintaining a good balance with other physical properties, it may be 2 ppm / °C or higher, 5 ppm / °C or higher, or 10 ppm / °C or higher. The thermal expansion coefficient of the cured prepreg can be measured by the method described in the examples.

[0116] <Uses of resin compositions> The resin composition of this embodiment is suitable as a resin composition for antenna modules because it is a resin composition with low thermal expansion while suppressing changes in the dielectric constant (Dk) of the cured product.

[0117] [Prepreg] The prepreg of this embodiment is a prepreg containing the resin composition of this embodiment. The prepreg of this embodiment is suitable as a prepreg for antenna modules. The prepreg of this embodiment is preferably obtained by impregnating or coating a sheet-like fibrous substrate with the resin composition of this embodiment, and then B-stage it. In this specification, B-stage refers to the state of B-stage as defined in JIS K 6900:1994, and is also called semi-curing.

[0118] As the sheet-like fibrous substrate contained in the prepreg of this embodiment, for example, a known sheet-like fibrous substrate used in laminates for various electrical insulating materials can be used. Examples of materials for sheet-like fiber substrates 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 substrates can take the form of woven fabrics, nonwoven fabrics, rawhide, chopped strand mats, and surfacing mats, for example. The thickness of the sheet-like fibrous base material is not particularly limited, but from the viewpoint of mechanical strength and thinning of the prepreg, it is preferably 0.01 to 0.5 mm, more preferably 0.02 to 0.3 mm, and even more preferably 0.03 to 0.1 mm. The sheet-like fibrous substrate may be surface-treated with a coupling agent or the like, or it may be mechanically opened, from the viewpoint of impregnation of the resin composition, heat resistance, moisture resistance when formed into a laminate, and processability.

[0119] The prepreg of this embodiment can be manufactured, for example, by impregnating or coating a sheet-like fibrous substrate with the resin composition of this embodiment, and then drying it as necessary. For example, the hot melt method, the solvent method, or the like can be used to impregnate or coat the resin composition of this embodiment onto a sheet-like fibrous substrate.

[0120] The hot melt method is a method of impregnating or coating a sheet-like fibrous substrate with a resin composition that does not contain organic solvents. One embodiment of the hot melt method involves first coating a coated paper with good release properties with the resin composition of this embodiment, which does not contain an organic solvent, and then laminating the coated resin composition onto a sheet-like fibrous substrate. Another aspect of the hot melt method is a method in which the resin composition of this embodiment, which does not contain an organic solvent, is directly applied to a sheet-like fibrous substrate using a die coater or the like.

[0121] The solvent method is a method of impregnating or coating a sheet-like fibrous substrate with a resin composition containing an organic solvent. Specifically, for example, one method involves immersing a sheet-like fibrous substrate in the resin composition of this embodiment containing an organic solvent, and then drying it. By drying, the organic solvent in the resin composition is removed, and the resin composition can be converted to the B-stage. The drying temperature is not particularly limited, but from the viewpoint of productivity and moderately B-stage the resin composition of this embodiment, it is preferably 50 to 200°C, more preferably 100 to 190°C, and even more preferably 150 to 180°C. The drying time is not particularly limited, but from the viewpoint of productivity and moderately B-stage the resin composition of this embodiment, it is preferably 1 to 30 minutes, more preferably 2 to 15 minutes, and even more preferably 3 to 10 minutes.

[0122] The solid content concentration derived from the resin composition in the prepreg of this embodiment is not particularly limited, but from the viewpoint of obtaining better moldability when it is made into a laminate, it is preferably 20 to 90% by mass, more preferably 25 to 80% by mass, and even more preferably 30 to 75% by mass.

[0123] The thickness of the prepreg in this embodiment is not particularly limited, but from the viewpoint of moldability and enabling high-density wiring, it is preferably 0.01 to 0.5 mm, more preferably 0.02 to 0.3 mm, and even more preferably 0.03 to 0.1 mm.

[0124] [Resin film] The resin film of this embodiment is a resin film containing the resin composition of this embodiment. The resin film of this embodiment is suitable as a resin film for antenna modules. The resin film of this embodiment can be manufactured, for example, by applying the resin composition of this embodiment, i.e., a resin varnish containing an organic solvent, to a support and then heating and drying it.

[0125] Examples of support materials include plastic film, metal foil, and release paper. Examples of plastic films include polyolefin films such as polyethylene, polypropylene, and polyvinyl chloride; polyester films such as polyethylene terephthalate (hereinafter sometimes referred to as "PET") and polyethylene naphthalate; polycarbonate films; and polyimide films. Among these, polyethylene terephthalate film is preferred from the viewpoint of economy and ease of handling. Examples of metal foils include copper foil and aluminum foil. When copper foil is used as the support, the copper foil can be used directly as the conductive layer to form a circuit. In this case, rolled copper foil, electrolytic copper foil, etc., can be used as the copper foil. When using thin copper foil, a carrier-attached copper foil may be used to improve workability. The support may be subjected to surface treatments such as matte finish or corona treatment. Furthermore, the support may be subjected to a release treatment using 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 from the viewpoint of handling and cost-effectiveness, it is preferably 10 to 150 μm, more preferably 20 to 100 μm, and even more preferably 25 to 50 μm.

[0126] 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 varnish can be appropriately determined according to the content and boiling point of the organic solvent, and are not particularly limited. For example, in the case of a resin varnish containing 40-60% by mass of an aromatic hydrocarbon solvent, the drying temperature is not particularly limited, but from the viewpoint of productivity and appropriately B-stage the resin composition of this embodiment, it is preferably 50-200°C, more preferably 100-190°C, and even more preferably 150-180°C. Furthermore, in the case of the resin varnish described above, the drying time is not particularly limited, but from the viewpoint of productivity and appropriately B-stage the resin composition of this embodiment, it is preferably 1 to 30 minutes, more preferably 2 to 15 minutes, and even more preferably 3 to 10 minutes.

[0127] The thickness of the resin film in this embodiment can be appropriately determined depending on the application of the resin film, but from the viewpoint of moldability and enabling high-density wiring, it is preferably 5 to 150 μm, more preferably 10 to 100 μm, and even more preferably 15 to 60 μm.

[0128] The resin film of this embodiment may have a protective film. The protective film is provided on the side of the resin film of this embodiment opposite to the side on which the support is provided, and is used to prevent foreign matter from adhering to the resin film and to prevent scratches. The protective film is peeled off before the resin film of this embodiment is laminated to a circuit board or the like by lamination, heat pressing, etc.

[0129] The resin film of this embodiment is preferably used to form an insulating layer when manufacturing a multilayer printed circuit board. The resin film of this embodiment, for example, when manufacturing a multilayer printed circuit board, melts and flows when laminated onto the circuit board, playing the role of embedding the circuit board. Furthermore, the resin film of this embodiment plays a role in filling through-holes, via holes, etc., present in a circuit board, by flowing into them.

[0130] [Laminated board] The laminate of this embodiment is a laminate containing the prepreg of this embodiment and metal foil. A laminate containing metal foil is sometimes referred to as a metal-clad laminate. The laminate of this embodiment is suitable as a laminate for antenna modules.

[0131] The metal used in the metal foil is not particularly limited and includes, for example, copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, and alloys containing one or more of these metal elements. Examples of alloys include copper-based alloys, aluminum-based alloys, and iron-based alloys. Examples of copper-based alloys include copper-nickel alloys. Examples of iron-based alloys include iron-nickel alloys. Among these, copper, nickel, aluminum, and iron-nickel alloys are preferred from the viewpoint of conductivity and availability, copper and aluminum are more preferred, and copper is even more preferred. The thickness of the metal foil is not particularly limited, but is preferably 1 to 200 μm, more preferably 2 to 100 μm, and even more preferably 3 to 50 μm.

[0132] 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. Typically, this heat-pressure molding process hardens the semi-cured prepreg to obtain the laminate of this embodiment. During heat and pressure molding, one prepreg sheet may be used, or two or more prepreg sheets may be laminated together. In addition to the prepreg and metal foil, a substrate with internal circuit processing may also be included in the heat and pressure molding process. For heat and pressure molding, for example, multi-stage presses, multi-stage vacuum presses, continuous molding machines, autoclave molding machines, etc., can be used. The heating temperature for heat-pressure molding is not particularly limited, but is preferably 100 to 300°C, more preferably 150 to 280°C, and even more preferably 200 to 250°C. The heating and pressing time for heating and pressing is not particularly limited, but is preferably 10 to 300 minutes, more preferably 30 to 200 minutes, and even more preferably 80 to 150 minutes. The pressure for heat-pressure molding is not particularly limited, but is preferably 1.5 to 5 MPa, more preferably 1.7 to 3 MPa, and even more preferably 1.8 to 2.5 MPa. However, these conditions can be adjusted as appropriate depending on the type of raw materials used, etc., and are not particularly limited.

[0133] [Multilayer printed circuit board] The multilayer printed circuit board of this embodiment contains one or more selected from the group consisting of the prepreg of this embodiment, the resin film of this embodiment, and the laminate of this embodiment. In other words, the multilayer printed circuit board of this embodiment includes at least a multilayer structure containing a cured prepreg of this embodiment, a cured resin film of this embodiment, or a laminate of this embodiment, and a conductor circuit layer. The multilayer printed circuit board of this embodiment is suitable as a multilayer printed circuit board for antenna modules. The following describes a method for manufacturing a multilayer printed circuit board according to this embodiment using the resin film of this embodiment.

[0134] When manufacturing a multilayer printed circuit board using the resin film of this embodiment, first, the resin film of this embodiment is laminated to one or both sides of the circuit board. After positioning the resin film of this embodiment so that it is in contact with the circuit board, the resin film of this embodiment can be laminated onto the circuit board by, for example, pressing it onto the circuit board while applying pressure and heating it using a vacuum laminator. Examples of circuit boards used in multilayer printed wiring boards include those with patterned conductive layers (circuits) formed on one or both sides of a glass epoxy, metal substrate, polyester substrate, polyimide substrate, BT resin substrate, thermosetting polyphenylene ether substrate, etc. The surface of the conductive layer of the circuit board may be pre-treated to roughen it, such as by blackening, from the viewpoint of adhesion.

[0135] Next, if necessary, the support of the resin film is peeled off, and then the resin film is heat-cured to form an insulating layer. The heating temperature for heat curing is not particularly limited, but is preferably 100 to 300°C, more preferably 120 to 280°C, and even more preferably 150 to 250°C. The heating time for heat curing is not particularly limited, but is preferably 2 to 300 minutes, more preferably 5 to 200 minutes, and even more preferably 10 to 150 minutes.

[0136] After forming the insulating layer by the method described above, drilling may be performed as needed. Drilling is a process of creating via holes, through holes, etc., in the circuit board and the formed insulating layer by methods such as drilling, laser, plasma, or a combination thereof. Examples of lasers used for drilling include carbon dioxide lasers, YAG lasers, UV lasers, and excimer lasers.

[0137] Next, the surface of the insulating layer may be roughened with an oxidizing agent. Furthermore, if via holes, through holes, etc., are formed in the insulating layer and the circuit board, the so-called "smear" generated during their formation may be removed with an oxidizing agent. The roughening treatment and smear removal can be performed simultaneously. The roughening treatment can create anchors of irregularities on the surface of the insulating layer. Examples of oxidizing agents include permanganates such as potassium permanganate and sodium permanganate, dichromates, ozone, hydrogen peroxide, sulfuric acid, and nitric acid. Among these, aqueous solutions of potassium permanganate and sodium permanganate are preferred, as these are commonly used oxidizing agents in the manufacture of multilayer printed circuit boards by the build-up method.

[0138] Next, a conductive layer is formed on the surface of the roughened insulating layer. The conductive layer can be formed, for example, by plating. Plating methods include, for example, electroless plating and electrolytic plating. Examples of metals for plating include copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, and alloys containing at least one of these metallic elements. Among these, copper and nickel are preferred, with copper being more preferred. Alternatively, a method can be employed in which a plating resist with a pattern reversed from the wiring pattern is formed first, and then the wiring pattern is formed solely by electroless plating. Furthermore, annealing may be performed after the conductor layer is formed. Annealing tends to further improve and stabilize the adhesive strength between the interlayer insulating layer and the conductor layer.

[0139] As a method for patterning the conductive layer and forming a circuit, known methods such as the subtractive method, the fully additive method, the semi-additive process (SAP), and the modified semi-additive process (m-SAP) can be used.

[0140] [Antenna equipment] The antenna device of this embodiment is an antenna device that includes the multilayer printed circuit board of this embodiment. The antenna device of this embodiment can be manufactured, for example, by mounting an antenna element on the multilayer printed circuit board of this embodiment. There are no particular restrictions on the method of installing the antenna elements, but it is preferable to arrange them in a two-dimensional array, for example. There are no particular restrictions on the configuration of the antenna device, but you can refer to, for example, Japanese Patent Publication No. 6777273.

[0141] [Antenna module] The antenna module of this embodiment is an antenna module that includes the antenna device of this embodiment and a power supply circuit. The antenna module of this embodiment can be manufactured, for example, by a method that includes installing a power supply circuit and the antenna device of this embodiment. While there are no particular restrictions on the power supply circuit, an RFIC (Radio Frequency Integrated Circuit) can be used. An RFIC includes switches, power amplifiers, low-noise amplifiers, attenuators, phase shifters, signal combiners / demultiplexers, mixers, and amplification circuits. The high-frequency signal supplied from the RFIC is transmitted to the feed point of the feed conductor via a short-circuit conductor formed in a via of the antenna module laminate. The configuration of the antenna module is not particularly limited, but you can refer to, for example, Japanese Patent Publication No. 6777273. [Examples]

[0142] The embodiment will be described in detail below with reference to examples. However, this embodiment is not limited to the following examples.

[0143] (Method for measuring weight-average molecular weight (Mw)) The weight-average molecular weight (Mw) was calculated from a calibration curve using standard polystyrene by gel permeation chromatography (GPC). The calibration curve was approximated by a cubic equation using standard polystyrene: TSKstandard 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 GPC measurement conditions are shown below. [GPC measurement conditions] Equipment: High-speed GPC equipment HLC-8320GPC Detector: UV-8320 ultraviolet absorption detector [manufactured by Tosoh Corporation] Columns: Guard column; TSK Guardcolumn SuperHZ-L+ column; TSKgel SuperHZM-N+ TSKgel SuperHZM-M+ TSKgel SuperH-RC (all manufactured by Tosoh Corporation, product names) Column sizes: 4.6 x 20 mm (guard column), 4.6 x 150 mm (column), 6.0 x 150 mm (reference column) Eluent: Tetrahydrofuran Sample concentration: 10 mg / 5 mL Injection volume: 25μL Flow rate: 1.00mL / min Measurement temperature: 40℃

[0144] ((B) Average particle size of titanium-based inorganic filler (D 50 (Measurement method) (B) Average particle size of titanium-based inorganic filler (D 50 For the measurement, 0.1 g of (B) titanium-based inorganic filler, which was the target of measurement, was diluted with 20 g of solvent (type: methyl ethyl ketone), and then dispersed by vibrating with a 100 W ultrasonic homogenizer for 5 to 20 minutes to prepare the measurement sample. One to two drops of the above sample were injected into the measurement cell, and the particle size distribution was measured at 25°C and a refractive index of 1.38 using a particle size distribution analyzer (Microtrac Bell Co., Ltd., product name: Microtrac MT3000) in accordance with the international standard ISO 13321. The particle size corresponding to 50% of the cumulative value (by volume) in the obtained particle size distribution was defined as the average particle size (D 50 )

[0145] ((B) Method for measuring the relative permittivity (Dk) of titanium-based inorganic filler at 10 GHz) (B) The relative permittivity (Dk) of the titanium-based inorganic filler at 10 GHz was measured using the following procedure. The titanium-based inorganic filler (B) and polyphenylene ether resin, which were the subjects of measurement, were blended in a ratio of 20% by volume of the titanium-based inorganic filler and 80% by volume of the polyphenylene ether resin, and then mixed. The resulting mixture was press-molded at 230°C for 30 minutes at 3 MPa to form a shape with a width of 50 mm, a length of 130 mm, and a thickness of 0.5 mm. Cut this into pieces measuring 0.5mm wide x 130mm long x 0.5mm thick. The resulting specimens were used to measure the relative permittivity (Dk). Next, using the test specimens obtained above, the relative permittivity (Dk) was measured by the cavity resonator perturbation method under the conditions of a frequency of 10 GHz and 25°C, using the following apparatus and program. • Measuring instrument: Agilent Technologies N5227A vector network analyzer • Cavity resonator: "CP129" (10GHz band resonator) manufactured by Kanto Electronics Applied Development Co., Ltd. • Measurement program: "CPMA-V2" manufactured by Kanto Electronics Applied Development Co., Ltd. The relative permittivity (Dk) of the test specimen measured above was taken as Dk1, and the relative permittivity (Dk) of the polyphenylene ether resin alone measured in advance under the above measurement conditions was taken as Dk2. Based on the following formula, the relative permittivity (Dk) of (B) the titanium-based inorganic filler alone was determined. Relative permittivity (Dk) = (Dk1 - Dk2 × 0.8 ) / 0.2

[0146] Manufacturing Example 1: Production of Aminomaleimide Compound 1 In a 5-liter reaction vessel capable of heating and cooling, equipped with a thermometer, stirrer, and moisture meter with reflux condenser, 195 parts by mass of 2,2-bis[4-(4-maleimidephenoxy)phenyl]propane, 44 parts by mass of 3,3'-diethyl-4,4'-diaminodiphenylmethane, 25 parts by mass of an amino-modified polysiloxane compound having primary amino groups at both ends (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "X-22-161B", primary amino group equivalent 1,500 g / mol), and 260 parts by mass of propylene glycol monomethyl ether were added and reacted under reflux for 2 hours. This was concentrated at reflux temperature for 3 hours to produce aminomaleimide compound 1 solution with a solid content of 65% by mass. Aminomaleimide compound 1 corresponds to aminomaleimide compound (AC). The weight-average molecular weight (Mw) of the obtained aminomaleimide compound 1 was approximately 2,200.

[0147] Manufacturing Example 2: Production of Aminomaleimide Compound 2 In the same manner as in Production Example 1, aminomaleimide compound 2 was obtained, except that an amino-modified polysiloxane compound having primary amino groups at both ends was not incorporated.

[0148] [Manufacturing of resin compositions] Examples 1-3, Comparative Examples 1-2 Each component listed in Table 1 was blended according to the proportions listed in Table 1, and then stirred and mixed at 25°C to prepare the resin composition. In Table 1, the unit for the amount of each component is parts by mass. Also, the amounts of components (A) and (C) listed in Examples 1 to 3 in Table 1 are parts by mass on a solid content basis when incorporated as the aminomaleimide compound 1 solution produced in Production Example 1. In other words, the amounts of components (A) and (C) listed in Examples 1 to 3 in Table 1 are the amounts of each component used in Production Example 1 described above. Furthermore, the (A) components listed in Comparative Examples 1 and 2 in Table 1 represent the parts by mass, on a solid content basis, of the aminomaleimide compound 2 solution prepared in Production Example 2. In other words, the amount of (A) components listed in Comparative Examples 1 and 2 in Table 1 corresponds to the amount of each component used in Production Example 2 described above.

[0149] [Manufacturing of resin films and resin sheets with copper foil on both sides] The resin composition obtained above was 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 resin film in the B-stage state. After peeling the resin film from the PET film, it was pulverized to obtain resin powder in the B-stage state. The resin powder obtained above was placed into a Teflon® sheet cut to a size of 0.5 mm thick x 50 mm long x 35 mm wide, and 18 μm thick low-profile copper foil (manufactured by Mitsui Mining & Smelting Co., Ltd., product name: 3EC-VLP-18) was placed above and below it. The low-profile copper foil was placed with its M-side facing the resin powder. Next, this laminate, before heat and pressure molding, was heat and pressure molded at a temperature of 230°C, a pressure of 2.0 MPa, and a time of 120 minutes, thereby curing the resin powder while molding it into a resin plate, and a double-sided copper foil-coated resin plate was produced. The thickness of the resin plate portion of the obtained double-sided copper foil-coated resin plate was 0.5 mm.

[0150] [Prepreg manufacturing] The resin composition obtained above was impregnated into a 0.1 mm thick E glass cloth and heated and dried at 110°C for 3 minutes to obtain a prepreg with a solid content of 48% by mass. Four of these prepregs were stacked, with 18 μm electrolytic copper foil placed above and below them, and the temperature was raised to 240°C at a pressure of 3.0 MPa and a heating rate of 4.0°C / min. After holding the temperature for 85 minutes, the pressure was released and the material was cooled for 30 minutes to obtain a copper-clad laminate.

[0151] [Measurement and evaluation 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 1.

[0152] (1. Measurement of gel time) 0.1 g of the resin powder in the B-stage state obtained above was placed on a hot plate at 160 °C, and the time until the resin hardened (gel time) was measured. The measured value was rounded to the nearest whole number for the average value of n = 2, and a gelation tester "GT-D-JIS" manufactured by Nissin Kagaku Co., Ltd. was used for the measurement. The gel time is preferably 450 seconds or more from the viewpoint of moldability.

[0153] (2. Measurement of relative permittivity (Dk)) After removing the outer copper foil of the resin plate with double-sided copper foil obtained above by immersing it in a copper etching solution (10% by mass solution of ammonium persulfate, manufactured by Mitsubishi Gas Chemical Co., Ltd.), a sample cut into a length of 60 mm and a width of 0.5 mm was used as a test piece for relative permittivity (Dk). Using this test piece, under the conditions of a frequency of 20 GHz and 25 °C, the relative permittivity (Dk) was measured by the cavity resonator perturbation method using the following device and program. · Measuring instrument: Vector network analyzer "N5227A" manufactured by Agilent Technologies · Cavity resonator: "CP" manufactured by Kanto Electronic Application Development Co., Ltd. 561 」( 2 0 GHz band resonator) · Measurement program: "CPMA-V2" manufactured by Kanto Electronic Application Development Co., Ltd.

[0154] (3. Measurement of thermal expansion coefficient) The outer copper foil of the copper-clad laminate obtained above was removed by immersing it in a copper etching solution (10% by mass solution of ammonium persulfate, manufactured by Mitsubishi Gas Chemical Co., Ltd.), and a 5 mm square test piece was prepared. Next, using a thermomechanical measurement device (TMA) (manufactured by TA Instruments Japan Co., Ltd., product name: Q400), in accordance with the IPC (The Institute for Interconnecting and Packaging Electronic Circuits) standard, the thermal expansion coefficient of the above test piece was measured. The thermal expansion coefficient is the thermal expansion coefficient in the thickness direction of the copper-clad laminate, and the average thermal expansion coefficient in the temperature range of 30 to 120 °C was used.

[0155]

Table 1

[0156] Incidentally, the details of component (B) shown in Table 1 are as follows. [Component (B)] · Calcium titanate 1: manufactured by Kyoritsu Materials Co., Ltd., trade name "CT-3", average particle diameter (D 50 ): 2 μm, relative permittivity (Dk) (10 GHz): 175 · Calcium titanate 2: manufactured by Sakai Chemical Industry Co., Ltd., trade name "CT-03", average particle diameter (D 50 ): 0.3 μm, relative permittivity (Dk) (10 GHz): 175 · Strontium titanate: manufactured by Sakai Chemical Industry Co., Ltd., trade name "ST-03", average particle diameter (D 50 ): 0.3 μm, relative permittivity (Dk) (10 GHz): 220

[0157] From Table 1, it can be seen that the resin compositions of Examples 1 to 3 of the present embodiment can reduce the thermal expansion coefficient without significantly changing the relative permittivity (Dk) of the cured product compared to the resin compositions of Comparative Examples 1 and 2 that did not contain component (C).

Industrial Applicability

[0158] The resin composition of the present embodiment is a resin composition with a reduced thermal expansion while suppressing the change in the relative permittivity (Dk) of the cured product. Therefore, the resin composition of the present embodiment is useful for multilayer printed wiring boards and the like used in fifth-generation mobile communication systems (5G) antennas where radio waves in a frequency band exceeding 6 GHz are used, and millimeter-wave radars where radio waves in a frequency band of 30 to 300 GHz are used.

Claims

1. (A) Thermosetting resin and (B) Titanium-based inorganic filler, (C) Siloxane compound having a reactive group, This is a resin composition for antenna modules comprising the following: (B) The content of the titanium-based inorganic filler is 40 to 80% by mass relative to the total solid content of the resin composition for the antenna module. The (A) thermosetting resin is a maleimide compound having one or more N-substituted maleimide groups, (C) The siloxane compound having a reactive group is an amino-modified siloxane compound having primary amino groups at both ends. A resin composition for antenna modules, comprising (C) a siloxane compound having a reactive group, which is reacted with (A) a thermosetting resin and then blended.

2. (B) Average particle size of titanium-based inorganic filler (D ５０ The resin composition for antenna modules according to claim 1, wherein the thickness of the diaphragm is 0.1 to 20 μm.

3. (B) The resin composition for an antenna module according to claim 1 or 2, wherein the relative permittivity (Dk) of the titanium-based inorganic filler at 10 GHz is 10 to 3,000.

4. (B) The resin composition for an antenna module according to any one of claims 1 to 3, wherein the titanium-based inorganic filler is a titanate.

5. The resin composition for antenna modules according to claim 4, wherein the titanate is one or more selected from the group consisting of barium titanate, potassium titanate, calcium titanate, strontium titanate, lead titanate, and aluminum titanate.

6. The resin composition for an antenna module according to any one of claims 1 to 5, wherein the maleimide compound having one or more N-substituted maleimide groups is an aromatic bismaleimide compound having two N-substituted maleimide groups.

7. The resin composition for an antenna module according to any one of claims 1 to 6, wherein the relative permittivity (Dk) of the cured product at 20 GHz is 2 to 50.

8. An antenna module prepreg comprising the resin composition for antenna modules described in any one of claims 1 to 7.

9. A laminate for an antenna module containing the antenna module prepreg and metal foil described in claim 8.

10. A multilayer printed wiring board for an antenna module comprising one or more selected from the group consisting of the prepreg for antenna modules described in claim 8 and the laminate for antenna modules described in claim 9.

11. An antenna device comprising a multilayer printed circuit board for an antenna module as described in claim 10.

12. An antenna module comprising the antenna device described in claim 11 and a power supply circuit.

13. (A) Thermosetting resin and (B) Titanium-based inorganic filler, (C) Siloxane compound having a reactive group, A prepreg containing a resin composition comprising the following: (B) The content of the titanium-based inorganic filler is 40 to 80% by mass relative to the total amount of solids in the resin composition. The (A) thermosetting resin is a maleimide compound having one or more N-substituted maleimide groups, (C) The siloxane compound having a reactive group is an amino-modified siloxane compound having primary amino groups at both ends. A prepreg obtained by reacting (C) a siloxane compound having a reactive group with (A) a thermosetting resin and then blending them together.

14. (B) Average particle size of titanium-based inorganic filler (D ５０ The prepreg according to claim 13, wherein the thickness is 0.1 to 20 μm.

15. (B) The prepreg according to claim 13 or 14, wherein the relative permittivity (Dk) of the titanium-based inorganic filler at 10 GHz is 10 to 3,000.

16. (B) The prepreg according to any one of claims 13 to 15, wherein the titanium-based inorganic filler is a titanate.

17. The prepreg according to claim 16, wherein the titanate is one or more selected from the group consisting of barium titanate, potassium titanate, calcium titanate, strontium titanate, lead titanate, and aluminum titanate.

18. The prepreg according to any one of claims 13 to 17, wherein the maleimide compound having one or more N-substituted maleimide groups is an aromatic bismaleimide compound having two N-substituted maleimide groups.

19. The prepreg according to any one of claims 13 to 18, wherein the relative permittivity (Dk) of the cured resin composition at 20 GHz is 2 to 50.

20. A laminate containing the prepreg and metal foil according to any one of claims 13 to 19.

21. A multilayer printed circuit board comprising one or more selected from the group consisting of a prepreg according to any one of claims 13 to 19 and a laminate according to claim 20.

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