Thermosetting resin composition, prepreg, resin film, laminate, printed wiring board, antenna device, antenna module, and communication device

Abstract

Provided is a thermosetting resin composition containing a high dielectric constant material, which is capable of suppressing the generation of outgassing, a decrease in heat resistance, and a decrease in peel strength when producing a cured product thereof. Also provided are a prepreg, a resin film, a laminate, a printed wiring board, an antenna device, an antenna module, and a communication device, each of which is obtained using the thermosetting resin composition. The thermosetting resin composition specifically contains (A) a thermosetting resin and (B) at least one high-dielectric-constant inorganic filler selected from the group consisting of titanium-based inorganic fillers and zirconium-based inorganic fillers, and further contains 1 part by mass or more of (C) a resin having 3% by mass or more of an acidic group per 100 parts by mass of the component (B).

Description

Technical Field

[0001] The present disclosure relates to a thermosetting resin composition, a prepreg, a resin film, a laminate, a printed wiring board, an antenna device, an antenna module, and a communication device. Background Art

[0002] In recent years, the popularity of mobile devices such as smartphones and the innovation and development of technologies such as IoT (Internet of Things) have resulted in an increase in the number of home appliances and electronic devices with wireless communication functions. As a result, there are concerns that the communication traffic of wireless networks will increase, and the communication speed and communication quality will decrease.

[0003] To solve this problem, the development of the fifth generation mobile communication system (hereinafter sometimes referred to as "5G") is underway and has gradually been used. In 5G, multiple antenna elements are used for advanced beamforming and spatial multiplexing. In addition to the signals of the 6 GHz band that have been used, higher frequency millimeter wave band signals of tens of GHz are also used. As a result, it is expected that the communication speed will be increased and the communication quality will be improved. In the following, 10 GHz and above are referred to as high frequency.

[0004] As described above, in the 5G state, the antenna module needs to be able to cope with high-frequency signals. To this end, the relative dielectric constant (Dk) and dielectric loss tangent (Df) of the laminate in the high-frequency band need to be low, especially the dielectric loss tangent (Df).

[0005] High-frequency radio waves have high linearity, so the signals carried by high-frequency radio waves tend to be easily blocked by obstacles such as buildings. Therefore, in order to avoid such blocking, multiple antenna devices are mounted on the antenna module. The antenna device can be miniaturized by increasing the relative dielectric constant (Dk) of the substrate material, so increasing the relative dielectric constant (Dk) is effective for multiple mountings of antenna devices and is associated with the miniaturization of the antenna module and even the miniaturization of the communication device. Therefore, it is required that the laminated board used for the antenna module capable of handling high-frequency signals has a specified high relative dielectric constant (Dk) and a low dielectric loss tangent (Df).

[0006] Here, as one method of increasing the relative dielectric constant (Dk) of the substrate material, a method of using a high dielectric constant material can be cited (for example, see Patent Document 1). The small antenna described in Patent Document 1 is manufactured by sandwiching a first dielectric layer containing a low dielectric constant material with a second and a third dielectric layer containing a high dielectric constant material and stacking them.

[0007] Prior art literature

[0008] Patent Literature

[0009] Patent Document 1: International Publication No. 2005 / 101574 Summary of the invention

[0010] Problems to be solved by the invention

[0011] Titanates and the like are known as high dielectric constant materials. However, the present inventors have found through research that if a thermosetting resin composition containing titanates and the like is placed under heating conditions in order to produce a cured product for an antenna device, problems such as (1) more outgassing (volatile gas) will occur, (2) the heat resistance of the cured product will decrease, and (3) the peel strength between the cured product and the copper foil (hereinafter referred to as "peel strength") will decrease, thereby reducing the reliability of the antenna device.

[0012] In view of this situation, the present disclosure aims to provide a thermosetting resin composition containing a high dielectric constant material, which can suppress the generation of outgassing, the reduction of heat resistance and the reduction of peel strength when manufacturing a cured product of the thermosetting resin composition; and provide a prepreg, a resin film, a laminate, a printed wiring board, an antenna device, an antenna module and a communication device obtained using the thermosetting resin composition.

[0013] Means for solving problems

[0014] The present inventors have conducted intensive studies and found that the above-mentioned object can be achieved by the thermosetting resin composition disclosed herein.

[0015] The present disclosure includes the following embodiments [1] to

[15] .

[0016] [1] A thermosetting resin composition comprising (A) a thermosetting resin and (B) at least one high dielectric constant inorganic filler selected from titanium-based inorganic fillers and zirconium-based inorganic fillers, and further comprising 1 part by mass or more of (C) a resin having 3% by mass or more of an acidic group, relative to 100 parts by mass of the component (B).

[0017] [2] The thermosetting resin composition according to [1], wherein the acidic group contained in the component (C) is at least one selected from the group consisting of a carboxylic anhydride group, a carboxyl group, a sulfone group and a phenolic hydroxyl group.

[0018] [3] The thermosetting resin composition according to [1] or [2], wherein the component (C) is a copolymer resin of an aromatic vinyl compound and maleic anhydride.

[0019] [4] The thermosetting resin composition according to any one of [1] to [3], wherein the titanium-based inorganic filler is at least one selected from titanium dioxide and metal titanate.

[0020] [5] The thermosetting resin composition according to [4], wherein the metal titanate is at least one selected from alkali metal titanates, alkaline earth metal titanates and lead titanate.

[0021] [6] The thermosetting resin composition according to any one of [1] to [5], wherein the zirconium-based inorganic filler is an alkali metal zirconate.

[0022] [7] The thermosetting resin composition according to any one of [1] to [6], wherein the content of the component (B) is 1 to 60% by volume based on the total solid content in the thermosetting resin composition.

[0023] [8] The thermosetting resin composition according to any one of [1] to [7], wherein the component (A) comprises at least one selected from epoxy resins, maleimide compounds, modified polyphenylene ether resins, phenolic resins, polyimide resins, cyanate resins, isocyanate resins, benzoxazine resins, oxetane resins, amino resins, unsaturated polyester resins, allyl resins, dicyclopentadiene resins, silicone resins, triazine resins and melamine resins.

[0024] [9] A prepreg comprising the thermosetting resin composition according to any one of [1] to [8] above or a semi-cured product of the thermosetting resin composition.

[0025]

[10] A resin film comprising the thermosetting resin composition according to any one of [1] to [8] above or a semi-cured product of the thermosetting resin composition.

[0026]

[11] A laminate comprising a cured product of the thermosetting resin composition according to any one of [1] to [8] above or a cured product of the prepreg according to [9] above, and a metal foil.

[0027]

[12] A printed wiring board comprising at least one selected from the group consisting of a cured product of the thermosetting resin composition described in any one of [1] to [8], a cured product of the prepreg described in [9], and a laminate described in

[11] .

[0028]

[13] An antenna device comprising the laminated board described in

[11] or the printed wiring board described in

[12] .

[0029]

[14] An antenna module comprising a power supply circuit and the antenna device described in

[13] above.

[0030]

[15] A communication device comprising a baseband signal processing circuit and the antenna module described in

[14] above.

[0031] Effects of the Invention

[0032] According to the present disclosure, a thermosetting resin composition containing a high dielectric constant material can be provided, and when a cured product of the thermosetting resin composition is produced, the generation of outgassing, the reduction in heat resistance and the reduction in peel strength can be suppressed, and a prepreg, a resin film, a laminate, a printed wiring board, an antenna device, an antenna module and a communication device obtained using the thermosetting resin composition can be provided. DETAILED DESCRIPTION

[0033] In the numerical range described in the present disclosure, the upper limit or lower limit of the numerical range can be replaced by the value shown in the embodiment. In addition, the lower limit and upper limit of the numerical range can be arbitrarily combined with the lower limit or upper limit of other numerical ranges, respectively. In the expression of the numerical range "AA to BB", the numerical values ​​AA and BB at both ends are included in the numerical range as the lower limit and upper limit, respectively.

[0034] In the present disclosure, for example, a description such as "10 or more" refers to 10 and values ​​exceeding 10, and this shall prevail even if the values ​​are different. In addition, for example, a description such as "10 or less" refers to 10 and values ​​less than 10, and this shall prevail even if the values ​​are different.

[0035] In addition, each component and material exemplified in this specification may be used alone or in combination of two or more unless otherwise specified. In this specification, when there are multiple substances corresponding to each component in the composition, the content of each component refers to the total amount of the multiple substances present in the composition unless otherwise specified.

[0036] In the present disclosure, the “resin component” refers to all components other than inorganic compounds such as a high dielectric constant inorganic filler and an inorganic filler described later, among the solid components constituting the resin composition.

[0037] In the present disclosure, "solid content" refers to components other than the organic solvent in the resin composition. In other words, the solid content includes not only solid substances at room temperature around 25°C but also liquid, syrupy or waxy substances at room temperature around 25°C.

[0038] The expression "containing XX" described in the present disclosure naturally includes the case where only XX is contained, but also includes the case where XX is contained in a state after reaction.

[0039] Arbitrary combinations of the matters described in the present disclosure are also included in the present disclosure and the embodiments.

[0040] [Thermosetting resin composition]

[0041] The thermosetting resin composition of this embodiment is as follows.

[0042] A thermosetting resin composition comprising:

[0043] (A) a thermosetting resin [hereinafter sometimes referred to as component (A)], and

[0044] (B) at least one high dielectric constant inorganic filler selected from titanium-based inorganic fillers and zirconium-based inorganic fillers [hereinafter sometimes referred to as component (B)],

[0045] Furthermore, 1 part by mass or more of (C) a resin having 3% by mass or more of an acidic group (hereinafter sometimes referred to as (C) component) is contained with respect to 100 parts by mass of the (B) component.

[0046] Hereinafter, the components contained in the thermosetting resin composition of this embodiment will be described in detail in order.

[0047] ((A) Thermosetting resin)

[0048] As component (A), epoxy resin, maleimide compound, modified polyphenylene ether resin, phenolic resin, polyimide resin, cyanate resin, isocyanate resin, benzoxazine resin, oxetane resin, amino resin, unsaturated polyester resin, allyl resin, dicyclopentadiene resin, silicone resin, triazine resin, melamine resin, etc. are listed. Among them, as component (A), epoxy resin, maleimide compound, polyphenylene ether resin is preferred, and epoxy resin and maleimide compound are more preferred from the viewpoint of low thermal expansion and heat resistance, and maleimide compound and polyphenylene ether resin are more preferred from the viewpoint of low thermal expansion and dielectric loss tangent (Df), etc.

[0049] (A) Component may be used alone or in combination of two or more.

[0050] As the epoxy resin, an epoxy resin having two or more epoxy groups in one molecule is preferred. Here, epoxy resins are classified into glycidyl ether type epoxy resins, glycidyl amine type epoxy resins, glycidyl ester type epoxy resins, etc. Among them, glycidyl ether type epoxy resins are preferred.

[0051] Epoxy resins can also be classified into various epoxy resins according to the different main skeletons. Among the above-mentioned types of epoxy resins, they are further classified into: bisphenol-type epoxy resins such as bisphenol A epoxy resin, bisphenol F epoxy resin, and bisphenol S epoxy resin; alicyclic epoxy resins such as dicyclopentadiene epoxy resin; aliphatic chain epoxy resins; phenolic epoxy resins such as phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F novolac type epoxy resin, phenol aralkyl novolac type epoxy resin, and biphenyl aralkyl novolac type epoxy resin; stilbene type epoxy resin; naphthalene skeleton-containing epoxy resins such as naphthol novolac type epoxy resin and naphthol aralkyl type epoxy resin; biphenyl aralkyl type epoxy resin; xylene type epoxy resin; dihydroanthracene type epoxy resin, etc.

[0052] The maleimide compound preferably contains at least one selected from maleimide compounds having one or more (preferably two or more) N-substituted maleimide groups and derivatives thereof.

[0053] As the maleimide compound having one or more N-substituted maleimide groups, although not particularly limited, examples thereof include: aromatic maleimide compounds preferably having one N-substituted maleimide group bonded to an aromatic ring, such as N-phenyl maleimide, N-(2-methylphenyl) maleimide, N-(4-methylphenyl) maleimide, N-(2,6-dimethylphenyl) maleimide, N-(2,6-diethylphenyl) maleimide, N-(2-methoxyphenyl) maleimide, N-benzyl maleimide; aromatic bismaleimide compounds preferably having two N-substituted maleimide groups bonded to an aromatic ring, such as bis(4-maleimidophenyl) methane, bis(4-maleimidophenyl) ether, bis(4-maleimidophenyl) sulfone, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, m-phenylene bismaleimide, 2,2-bis[4-(4-maleimidophenoxy)phenyl] propane, bismaleimide containing an indane ring; aromatic polymaleimide compounds preferably having three or more N-substituted maleimide groups bonded to an aromatic ring, such as polyphenylmethane maleimide, biphenyl aralkyl type maleimide; aliphatic maleimide compounds such as N-dodecyl maleimide, N-isopropyl maleimide, N-cyclohexyl maleimide, 1,6-bis maleimide-(2,2,4-trimethyl) hexane, long-chain alkyl bismaleimide of pyrophosphate binder type (Japanese: ピロリロン酸バインダ型). Among them, from the viewpoints of compatibility with other resins, peel strength, heat resistance, low thermal expansion property, and mechanical properties, more preferably, aromatic bismaleimide compounds preferably having two N-substituted maleimide groups bonded to an aromatic ring are further preferably 2,2-bis[4-(4-maleimidophenoxy)phenyl] propane.

[0054] The maleimide compound having one or more N-substituted maleimide groups may be a maleimide compound having two or more N-substituted maleimide groups. In this case, in the maleimide compound having two or more N-substituted maleimide groups, it is preferable that the nitrogen atoms of at least two maleimide groups are connected to each other through an organic group. Examples of the above organic group include: groups such as aliphatic hydrocarbon groups, aromatic hydrocarbon groups, heteroaromatic hydrocarbon groups, and combinations thereof that may contain heteroatoms.

[0055] It should be noted that derivatives of maleimide compounds include: addition reaction products of the maleimide compounds having one or more (preferably two or more) N-substituted maleimide groups and amine compounds such as monoamine compounds and diamine compounds (hereinafter sometimes referred to as "modified maleimide compounds"), etc. Examples of the monoamine compounds include: monoamine compounds having acidic substituents such as o-aminophenol, m-aminophenol, p-aminophenol, o-aminobenzoic acid, m-aminobenzoic acid, p-aminobenzoic acid, o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, and 3,5-dicarboxyaniline. Examples of the diamine compound include 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenylpropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis(4,4'-diaminodiphenyl)propane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylethane, 3,3'-diethyl-4,4'-diaminodiphenylethane, Diphenylethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,3'-dihydroxy-4,4'-diaminodiphenylmethane, 2,2',6,6'-tetramethyl-4,4'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 3,3'-dibromo-4,4'-diaminodiphenylmethane, 2,2',6,6'-tetrachloro-4,4'-diaminodiphenylmethane, 2,2',6,6'-tetrabromo-4,4'-diaminodiphenylmethane, siloxane diamine, etc. Among them, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, and siloxane diamine are preferred.

[0056] The monoamine compound and the diamine compound may be used alone or in combination of two or more.

[0057] The maleimide compound is preferably an addition reaction product of a maleimide compound having two or more N-substituted maleimide groups and an amine compound, more preferably an addition reaction product of a maleimide compound having two or more N-substituted maleimide groups and a diamine compound, and further preferably an addition reaction product of a maleimide compound having two or more N-substituted maleimide groups and a diamine compound comprising siloxane diamine.

[0058] The modified polyphenylene ether resin is preferably a polyphenylene ether resin having a group containing an ethylenically unsaturated bond at the end, and more preferably a polyphenylene ether resin having a group containing an ethylenically unsaturated bond at both ends. Here, "group containing an ethylenically unsaturated bond" refers to a substituent containing a carbon-carbon double bond capable of an addition reaction, excluding double bonds of aromatic rings. As the group containing an ethylenically unsaturated bond, it can be cited; unsaturated aliphatic hydrocarbon groups such as vinyl, allyl, 1-methylallyl, isopropenyl, 2-butenyl, 3-butenyl, styryl, etc.; maleimide, (meth) acryloyl, etc., containing heteroatoms and ethylenically unsaturated bonds, etc. As a group containing an ethylenically unsaturated bond, it is preferably a group containing heteroatoms and ethylenically unsaturated bonds, more preferably a (meth) acryloyl, and further preferably a methacryloyl.

[0059] In addition, in this disclosure, "(meth)acryloyl group" means an acryloyl group or a methacryloyl group.

[0060] (Content of component (A))

[0061] The content of the (A) thermosetting resin in the thermosetting resin composition of the present embodiment is not particularly limited, but from the viewpoint of dielectric loss tangent (Df), heat resistance and formability, it is preferably 5 to 95 parts by mass, more preferably 10 to 80 parts by mass, further preferably 10 to 60 parts by mass, and particularly preferably 15 to 40 parts by mass, relative to 100 parts by mass of the total solid content in the thermosetting resin composition.

[0062] ((B) at least one high dielectric constant inorganic filler selected from titanium-based inorganic fillers and zirconium-based inorganic fillers)

[0063] As the titanium-based inorganic filler, from the viewpoint of relative dielectric constant (Dk), it is preferably at least one selected from titanium dioxide and metal titanate. As the metal titanate, from the viewpoint of relative dielectric constant (Dk), there can be cited: alkali metal titanate such as potassium titanate; alkaline earth metal titanate such as barium titanate, calcium titanate, strontium titanate; lead titanate, etc. As the metal titanate, it is preferably at least one selected from these examples, and from the viewpoint of relative dielectric constant (Dk), it is more preferably an alkaline earth metal titanate, and more preferably calcium titanate and strontium titanate.

[0064] The zirconium-based inorganic filler is preferably an alkali metal zirconate from the viewpoint of relative dielectric constant (Dk). The alkali metal zirconate is preferably at least one selected from calcium zirconate and strontium zirconate from the viewpoint of relative dielectric constant (Dk).

[0065] As the component (B), from the viewpoint of dielectric loss tangent (Df) and specific gravity, a titanium-based inorganic filler is preferred, and the above-mentioned ones are more preferred.

[0066] The average particle size of the component (B) is not particularly limited, but is preferably 0.1 μm or more, more preferably 0.4 μm or more, more preferably 1.0 μm or more, and particularly preferably 1.5 μm or more from the viewpoint of heat resistance. The upper limit of the average particle size of the component (B) is preferably 4.5 μm or less, more preferably 4.0 μm or less, further preferably 3.5 μm or less, particularly preferably 3.0 μm or less, and most preferably 2.5 μm or less from the viewpoint of excluding coarse particles that may cause poor insulation.

[0067] According to the above description, the average particle size of the component (B) is preferably 0.1 to 4.5 μm, and the lower limit and upper limit of the numerical range can be changed based on the above description.

[0068] Here, in the present disclosure, the average particle size refers to the average primary particle size.

[0069] In the present disclosure, the average particle size is the value of d50 (median particle size of volume distribution) obtained by analyzing the particle size distribution using a particle size distribution measuring device. The method and conditions for analyzing the particle size distribution may be specifically described in the examples.

[0070] The shape of the component (B) is not particularly limited. Since most industrially available high dielectric constant inorganic fillers are generally amorphous, the shape may be amorphous, but other shapes such as spherical may also be used.

[0071] (Content of component (B))

[0072] The content of the component (B) in the thermosetting resin composition of the present embodiment is not particularly limited, but from the viewpoint of relative dielectric constant (Dk), it is preferably 1 to 60% by volume, more preferably 2 to 30% by volume, 3 to 20% by volume, 7 to 30% by volume, or 12 to 25% by volume relative to the total solid content in the thermosetting resin composition. If the content of the component (B) is recorded in parts by mass, it is preferably 5 to 95 parts by mass, more preferably 15 to 90 parts by mass, further preferably 20 to 70 parts by mass, particularly preferably 20 to 55 parts by mass, and most preferably 25 to 50 parts by mass relative to 100 parts by mass of the total solid content in the thermosetting resin composition.

[0073] When the content of the component (B) in the thermosetting resin composition of the present embodiment is at least the above lower limit, the relative dielectric constant (Dk) tends to be sufficiently increased, while when it is at most the above upper limit, the dielectric loss tangent (Df) tends to be suppressed from being too high.

[0074] ((C) Resin having 3% by mass or more of acidic groups)

[0075] The thermosetting resin composition of the present embodiment contains 1 part by mass or more of a resin having an acidic group of 3% or more as the (C) component relative to 100 parts by mass of the above-mentioned (B) component. Thus, even if the thermosetting resin composition of the present embodiment contains the above-mentioned (B) component, when manufacturing the cured product of the thermosetting resin composition, it is possible to suppress the generation of outgassing, the reduction of heat resistance and the reduction of peel strength. It is speculated that the reason for obtaining this effect is that by making the thermosetting composition contain a resin having an acidic group of more than a specified amount, the alkalinity tendency of the thermosetting composition caused by the (B) component is suppressed, the surface activity (catalytic activity) of the (B) component is reduced, and thus the decomposition (breakage of molecular bonds) of the (A) component and the degradation of the (A) component are suppressed. However, even if this inference is incorrect, this matter will not affect the scope of the present disclosure.

[0076] In order to obtain the above-mentioned effect, as component (C), the content of the acidic group in the resin (component (C)) is 3 mass parts or more, and the component (C) contains 1 mass part or more relative to 100 mass parts of the above-mentioned component (B). In order to obtain the above-mentioned effect, the content of the acidic group is preferably 3 to 40 mass%, more preferably 5 to 35 mass%, further preferably 7 to 30 mass%, and particularly preferably 9 to 25 mass%. It should be noted that by making the content of the acidic group less than 40 mass% in the resin (component (C)), there is a tendency to suppress the deterioration of compatibility with other resins and the reduction of heat resistance. Here, the content of the above-mentioned acidic group is a value calculated by titration, and more specifically, it can be measured by the method described in the examples.

[0077] In addition, in order to obtain the above-mentioned effect, it is preferred that the (C) component contains 1 to 40 parts by mass relative to 100 parts by mass of the (B) component, more preferably 2 to 35 parts by mass, further preferably 3 to 30 parts by mass, and particularly preferably 3 to 25 parts by mass. It should be noted that by making the (C) component 40 parts by mass or less relative to 100 parts by mass of the (B) component, the dispersibility of the (C) component is excellent, and it is also possible to suppress the decrease in flame retardancy and the tendency of the dielectric loss tangent (Df) to be too high.

[0078] The acidic group of the component (C) is preferably at least one selected from a carboxylic anhydride group, a carboxyl group, a sulfone group and a phenolic hydroxyl group, more preferably at least one selected from a carboxylic anhydride group and a carboxyl group, and still more preferably a carboxylic anhydride group.

[0079] Specifically, the component (C) is preferably a copolymer resin of an aromatic vinyl compound and maleic anhydride [hereinafter sometimes referred to as copolymer resin (C-1)]. Examples of the aromatic vinyl compound include styrene, 1-methylstyrene, vinyltoluene, dimethylstyrene, etc. The aromatic vinyl compound preferably contains styrene.

[0080] The copolymer resin (C-1) may be a material obtained by copolymerizing various polymerizable components in addition to the aromatic vinyl compound and maleic anhydride. Examples of the various polymerizable components include vinyl compounds such as ethylene, propylene, butadiene, isobutylene, and acrylonitrile; and compounds having a (meth)acryloyl group such as methyl acrylate and methyl methacrylate.

[0081] The copolymer resin (C-1) may further have a substituent such as an alkenyl group such as an allyl group, a (meth)acryloyl group, a hydroxyl group, etc. The substituent can be introduced into the copolymer resin (C-1) by a Friedel-Crafts reaction or a reaction using a metal catalyst such as lithium.

[0082] In the copolymer resin (C-1), the content ratio of the aromatic vinyl compound unit to the maleic anhydride unit [aromatic vinyl compound unit / maleic anhydride unit] (molar ratio) is preferably 2 to 12, more preferably 3 to 10. When the content ratio is 2 or more, the heat resistance tends to be sufficient, while when it is 12 or less, the generation of outgassing is easily suppressed, the heat resistance is reduced, the peel strength is reduced, and the dielectric loss tangent (Df) tends to be too high.

[0083] The total content of the aromatic vinyl compound unit and the maleic anhydride unit in the copolymer resin (C-1) is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 90% by mass or more, and particularly preferably 100% by mass, from the viewpoint of suppressing the generation of outgassing, reduction in heat resistance and reduction in peel strength.

[0084] The weight average molecular weight (Mw) of the component (C) and the copolymer resin (C-1) is preferably 5000 to 18000, more preferably 6000 to 17000, further preferably 8000 to 16000, particularly preferably 9000 to 16000, and may be 10000 to 16000, 9000 to 12500, or 12500 to 16000. It should be noted that the weight average molecular weights in the present disclosure are all values ​​measured by gel permeation chromatography (GPC) (standard polystyrene conversion) using tetrahydrofuran as an eluent.

[0085] The thermosetting resin composition of the present embodiment may further contain other components. As other components, although not particularly limited, they preferably include: one or more selected from (D) elastomer, (E) inorganic filler [but excluding (B) component], coupling agent, (F) curing accelerator, (G) antioxidant, (H) flame retardant, flame retardant auxiliary, adhesion enhancer, heat stabilizer, antistatic agent, ultraviolet absorber, pigment, colorant and lubricant.

[0086] ((D) Elastomer)

[0087] The thermosetting resin composition of the present embodiment is not particularly limited, but preferably further contains (D) an elastomer. The component (D) does not include the component (C) described above.

[0088] Examples of the elastomer (D) include styrene elastomers, olefin elastomers, urethane elastomers, polyester elastomers, polyamide elastomers, acrylic elastomers, and silicone elastomers. These elastomers are composed of a hard segment component and a soft segment component. Generally speaking, the hard segment component contributes to heat resistance and strength, and the soft segment component contributes to flexibility and toughness.

[0089] (D) The elastomer may be used alone or in combination of two or more.

[0090] As the above-mentioned (D) elastomer, from the viewpoint of dielectric loss tangent (Df), preferably a styrene elastomer, more preferably a styrene thermoplastic elastomer. As a styrene elastomer, having a structural unit from a styrene compound, from the viewpoint of dielectric loss tangent (Df), peel strength, heat resistance and low thermal expansion, preferably selected from styrene-butadiene-styrene block copolymer hydride (SEBS) and styrene-isoprene-styrene block copolymer hydride (SEPS) One or more. More preferably a styrene-butadiene-styrene block copolymer hydride (SEBS).

[0091] It should be noted that the styrene elastomer may also be an elastomer modified by an acid anhydride such as maleic anhydride. For example, SEBS modified by an acid anhydride such as maleic anhydride, SEPS modified by an acid anhydride such as maleic anhydride, etc. The acid value of the acid-modified styrene elastomer is not particularly limited, but is preferably 2 to 20 mgCH3ONa / g, more preferably 5 to 15 mgCH3ONa / g, and further preferably 7 to 13 mgCH3ONa / g.

[0092] In the styrene-based elastomer, the content of the structural unit derived from styrene [hereinafter sometimes referred to as "styrene content"] is not particularly limited, but from the viewpoint of dielectric loss tangent (Df), peel strength, heat resistance and low thermal expansion, it is preferably 5 to 80 mass %, more preferably 10 to 75 mass %, further preferably 15 to 60 mass %, and particularly preferably 20 to 45 mass %.

[0093] The weight average molecular weight (Mw) of the styrene elastomer is not particularly limited, but is preferably 12,000 to 1,000,000, more preferably 30,000 to 500,000, further preferably 50,000 to 120,000, and particularly preferably 70,000 to 100,000. The weight average molecular weight (Mw) refers to a value measured by gel permeation chromatography (GPC) in terms of polystyrene.

[0094] ((D) Elastomer content)

[0095] When the thermosetting resin composition of the present embodiment contains (D) elastomer, the content thereof is not particularly limited, but is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, and further preferably 1.0 to 10 parts by mass relative to 100 parts by mass of the total solid content in the thermosetting resin composition. If the content of (D) elastomer is above the above lower limit, there is a tendency to obtain a more excellent dielectric loss tangent (Df), and if it is below the above upper limit, there is a tendency to obtain good heat resistance, formability, processability, and flame retardancy.

[0096] ((E) Inorganic filler)

[0097] The thermosetting resin composition of the present embodiment is not particularly limited, but preferably further contains (E) an inorganic filler.

[0098] The thermosetting resin composition of this embodiment tends to obtain more excellent low thermal expansion, high elastic modulus, heat resistance and flame retardancy by containing the (E) inorganic filler. However, the (E) inorganic filler does not include the above-mentioned (B) component.

[0099] (E) The inorganic filler may be used alone or in combination of two or more.

[0100] As (E) inorganic filler, there can be mentioned: silica, alumina, mica, beryllium oxide, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clays such as calcined clay, molybdate compounds such as zinc molybdate, talc, aluminum borate, silicon carbide, etc. Among them, from the viewpoint of low thermal expansion, elastic modulus, heat resistance and flame retardancy, preferably silica, alumina, mica, talc, more preferably silica, alumina, further preferably silica. As silica, there can be mentioned: crushed silica, fumed silica, fused silica, etc. Among them, preferably fused silica, more preferably fused spherical silica.

[0101] The average particle size of the (E) inorganic filler is not particularly limited, but is preferably 0.01 to 20 μm, more preferably 0.1 to 10 μm, further preferably 0.2 to 3 μm, and particularly preferably 0.3 to 1.0 μm.

[0102] ((E) Content of inorganic filler)

[0103] When the thermosetting resin composition of the present embodiment contains (E) an inorganic filler, the content thereof is not particularly limited, but in any case, from the viewpoint of thermal expansion coefficient, elastic modulus, heat resistance and flame retardancy, it is preferably 3 to 70 volume %, more preferably 5 to 65 volume %, further preferably 5 to 60 volume %, further preferably 10 to 50 volume %, particularly preferably 10 to 40 volume %, and most preferably 10 to 30 volume % relative to the total solid content in the thermosetting resin composition.

[0104] When the content of the component (E) is described in parts by mass, it is preferably 1 to 60 parts by mass, more preferably 5 to 50 parts by mass, further preferably 10 to 45 parts by mass, particularly preferably 15 to 45 parts by mass, and most preferably 20 to 40 parts by mass, relative to 100 parts by mass of the total solid content in the thermosetting resin composition.

[0105] When an inorganic filler is used, a coupling agent may be used in combination as needed to improve the dispersibility of the inorganic filler and the adhesion between the inorganic filler and the organic component in the resin composition. As coupling agents, silane coupling agents, titanate coupling agents, etc. may be mentioned. One coupling agent may be used alone, or two or more coupling agents may be used in combination.

[0106] When a coupling agent is used, the treatment method may be a so-called integral mixing method in which the coupling agent is added after the inorganic filler is mixed with the resin composition, but it is preferably a method in which the inorganic filler is surface-treated in advance with a coupling agent in a dry or wet manner. By adopting this method, the characteristics of the inorganic filler can be more effectively utilized.

[0107] Alternatively, the inorganic filler may be used in the form of a slurry dispersed in an organic solvent in advance, as necessary.

[0108] ((F) Curing accelerator)

[0109] The thermosetting resin composition of the present embodiment is not particularly limited, but preferably further contains (F) a curing accelerator.

[0110] As the above-mentioned (F) curing accelerator, there can be mentioned: amine curing accelerator, imidazole curing accelerator, phosphorus curing accelerator, organic metal salt, acid catalyst, organic peroxide, etc. It should be noted that in the present embodiment, imidazole curing accelerator is not classified into amine curing accelerator. One kind of curing accelerator can be used alone, or two or more kinds can be used in combination. As curing accelerator, preferably amine curing accelerator, imidazole curing accelerator, phosphorus curing accelerator.

[0111] Examples of the amine-based curing accelerator include amine compounds having a primary, secondary or tertiary amino group, such as triethylamine, 4-aminopyridine, tributylamine and dicyandiamide; and quaternary ammonium compounds.

[0112] Examples of the imidazole curing accelerator include imidazole compounds such as methylimidazole, phenylimidazole, 2-undecylimidazole, and isocyanate-masked imidazole (for example, an addition reaction product of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole).

[0113] Examples of the phosphorus-based curing accelerator include tertiary phosphines such as triphenylphosphine and quaternary phosphorus compounds such as tri-n-butylphosphine addition reaction products of p-benzoquinone and the like.

[0114] ((F) Content of curing accelerator)

[0115] When the thermosetting resin composition of the present embodiment contains (F) a curing accelerator, the content thereof is not particularly limited, but in any case, it is preferably 0.01 to 3 parts by mass, more preferably 0.05 to 2.5 parts by mass, further preferably 0.1 to 2.5 parts by mass, and particularly preferably 0.5 to 2.3 parts by mass relative to 100 parts by mass of the total resin components in the thermosetting resin composition. If the content of the (F) curing accelerator is within the above range, there is a tendency to obtain better dielectric loss tangent (Df), heat resistance, storage stability, and formability.

[0116] ((G) Antioxidant)

[0117] The thermosetting resin composition of the present embodiment is not particularly limited, but preferably further contains (G) an antioxidant.

[0118] The antioxidant is not particularly limited, but examples thereof include phenolic antioxidants such as hindered phenolic antioxidants and styrenated phenolic antioxidants.

[0119] ((G) Antioxidant content)

[0120] When the thermosetting resin composition of the present embodiment contains (G) an antioxidant, the content thereof is not particularly limited, but in any case, it is preferably 0.01 to 3 parts by mass, more preferably 0.05 to 2.5 parts by mass, further preferably 0.1 to 2.0 parts by mass, and particularly preferably 0.5 to 1.5 parts by mass relative to 100 parts by mass of the total solid content in the thermosetting resin composition. If the content of the (G) antioxidant is within the above range, the storage stability of the varnish described later becomes good, and it is easy to suppress the decrease in heat resistance, the decrease in peel strength, and the tendency of the dielectric loss tangent (Df) to be too high.

[0121] ((H) Flame retardant)

[0122] The thermosetting resin composition of the present embodiment is not particularly limited, but preferably further contains (H) a flame retardant.

[0123] Examples of the flame retardant (H) include inorganic phosphorus flame retardants, organic phosphorus flame retardants, and metal hydrates such as aluminum hydroxide hydrates and magnesium hydroxide hydrates. It should be noted that although metal hydroxides can also meet the requirements of the inorganic filler, they are classified as flame retardants in the case of metal hydroxides that can impart flame retardancy. Among them, the flame retardant (H) is preferably an organic phosphorus flame retardant.

[0124] Examples of organic phosphorus flame retardants include aromatic phosphates, phosphonic acid diesters and phosphinates; metal salts of phosphinates, organic nitrogen-containing phosphorus compounds, cyclic organic phosphorus compounds, etc. Here, "metal salts" include lithium salts, sodium salts, potassium salts, calcium salts, magnesium salts, aluminum salts, titanium salts, zinc salts, etc. Among them, aromatic phosphates are preferred as organic phosphorus flame retardants.

[0125] ((H) Content of flame retardant)

[0126] When the thermosetting resin composition of the present embodiment contains (H) a flame retardant, its content is not particularly limited, but in any case, relative to the total of 100 parts by mass of the solid components in the thermosetting resin composition, it is preferably 0.1 to 30 parts by mass, or 1 to 25 parts by mass, or 3 to 20 parts by mass, or 5 to 15 parts by mass. If the content of the (H) flame retardant is above the above lower limit, there is a tendency to obtain better flame retardancy. If it is below the above upper limit, there is a tendency to obtain better formability, peel strength, and better heat resistance.

[0127] (Contents of ingredients other than the above ingredients)

[0128] When the thermosetting resin composition of the present embodiment contains components other than the above-mentioned components (flame retardant aids, adhesion improvers, heat stabilizers, antistatic agents, ultraviolet absorbers, pigments, colorants, lubricants, and components other than these), the content of each component is not particularly limited, but relative to 100 parts by mass of the total resin components of the thermosetting resin composition, for example, it can be more than 0.01 parts by mass, or it can be less than 10 parts by mass, or it can be less than 5 parts by mass, or it can be less than 1 part by mass, or it can be not contained.

[0129] (Organic Solvent)

[0130] The thermosetting resin composition of the present embodiment may be a so-called “varnish” containing an organic solvent from the viewpoint of easy handling and easy production of a prepreg described later.

[0131] Although there is no particular limitation on the organic solvent, examples thereof include: alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene, and mesitylene; nitrogen-containing solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; sulfur-containing solvents such as dimethyl sulfoxide; ester solvents such as γ-butyrolactone, etc. From the viewpoint of solubility, a ketone solvent is preferred, and methyl isobutyl ketone is more preferred. The organic solvent may be used alone or in combination of two or more.

[0132] When the thermosetting resin composition of the present embodiment is used as a varnish, the solid content concentration is preferably set to 30 to 90% by mass, more preferably 40 to 80% by mass, and further preferably 55 to 70% by mass. If the solid content concentration of the thermosetting resin composition is within the above range, the handleability of the thermosetting resin composition becomes easy, the impregnation property into the substrate and the appearance of the manufactured prepreg become good, and the coating property when made into a resin film also becomes good.

[0133] The thermosetting resin composition of the present embodiment can be prepared by mixing the components (A) to (C) and the above-mentioned components that can be used as needed by a known method. At this time, each component can be dissolved or dispersed in the above-mentioned organic solvent while stirring. The conditions such as the mixing order, temperature, and time are not particularly limited and can be set arbitrarily.

[0134] Since the thermosetting resin composition of this embodiment can exhibit a high relative dielectric constant (Dk) and a low dielectric loss tangent (Df), it is useful for antenna modules, especially for miniaturized antenna modules corresponding to the fifth generation mobile communication system (5G).

[0135] [Prepreg]

[0136] The prepreg of the present embodiment is a prepreg containing the thermosetting resin composition of the present embodiment or a semi-cured product of the thermosetting resin composition described above.

[0137] The prepreg of the present embodiment, for example, contains the thermosetting resin composition of the present embodiment or a semi-cured product of the above-mentioned thermosetting resin composition and a sheet-like fiber substrate. The prepreg is formed using the thermosetting resin composition of the present embodiment and the sheet-like fiber substrate, and can be obtained, for example, by the following method: the thermosetting resin composition of the present embodiment is impregnated or applied to the sheet-like fiber substrate, dried and semi-cured (B-staged) as needed. More specifically, the prepreg of the present embodiment can be prepared, for example, by the following method: generally, it is heated and dried in a drying furnace at a temperature of 80 to 200° C. for 1 to 30 minutes to semi-cure (B-staged). Here, B-staged in the present disclosure means: reaching the B-stage state defined in JIS K6900 (1994).

[0138] The amount of the thermosetting resin composition used can be appropriately determined for the purpose of making the solid content concentration of the thermosetting resin composition in the dried prepreg reach 30 to 90% by mass. By making the solid content concentration within the above range, there is a tendency to obtain better formability when making a laminate.

[0139] As the sheet-like fiber substrate of the prepreg, known materials used in various laminates for electrical insulating materials can be used. Examples of the material of the sheet-like fiber substrate 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 have, for example, a woven fabric, a nonwoven fabric, a roving, a chopped strand mat, or a surface mat.

[0140] The thickness of the prepreg is not particularly limited, and may be 10 to 170 μm, 10 to 120 μm, or 10 to 70 μm.

[0141] Since the prepreg of this embodiment can exhibit a high relative dielectric constant (Dk) and a low dielectric loss tangent (Df), it is useful for antenna modules, especially for miniaturized antenna modules that cope with 5G.

[0142] [Resin film]

[0143] The resin film of the present embodiment is a resin film containing the thermosetting resin composition of the present embodiment or a semi-cured product of the thermosetting resin composition.

[0144] The resin film of the present embodiment can be produced, for example, by applying a thermosetting resin composition containing an organic solvent, that is, a varnish, to a support, heating and drying it, and semi-curing (B-stage) it as needed.

[0145] Examples of the support include plastic films, metal foils, and release papers.

[0146] The drying temperature and drying time may be appropriately determined depending on the amount of the organic solvent used and the boiling point of the organic solvent used. A resin film can be suitably formed by drying at 50 to 200° C. for about 1 to 10 minutes.

[0147] Since the resin film of this embodiment can exhibit a high relative dielectric constant (Dk) and a low dielectric loss tangent (Df), it is useful for antenna modules, especially for miniaturized antenna modules corresponding to 5G.

[0148] [Laminated board]

[0149] The laminated plate of the present embodiment is a laminated plate including a cured product of the thermosetting resin composition of the present embodiment or a cured product of the prepreg and a metal foil.

[0150] The laminated plate of the present embodiment can be manufactured, for example, by configuring a metal foil on one or both sides of a prepreg obtained by overlapping two or more prepregs of the present embodiment, or configuring a metal foil on one or both sides of a prepreg obtained by overlapping two or more prepregs of the present embodiment and prepregs other than the present embodiment, followed by heating and pressurizing. In the laminated plate obtained by this manufacturing method, the prepreg of the present embodiment is C-staged. In the present disclosure, C-stage refers to: reaching the C-stage state defined in JIS K6900 (1994). It should be noted that a laminated plate having a metal foil is sometimes also referred to as a metal-clad laminated plate.

[0151] The metal used as the metal foil is not particularly limited, but from the perspective of conductivity, it can be copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, or an alloy containing one or more of these metal elements, preferably copper and aluminum, and more preferably copper.

[0152] The conditions for heat and pressure forming are not particularly limited, but can be carried out, for example, at a temperature of 100 to 300° C., a pressure of 0.2 to 10 MPa, and a time of 0.1 to 5 hours. In addition, heat and pressure forming can be carried out by maintaining a vacuum state for 0.5 to 5 hours using vacuum pressing or the like.

[0153] Since the laminated plate of this embodiment has a high relative dielectric constant (Dk) and a low dielectric loss tangent (Df), it is useful for antenna modules, especially for miniaturized antenna modules that cope with 5G.

[0154] [Printed wiring board]

[0155] The printed wiring board of the present embodiment has one or more selected from the cured product of the thermosetting resin composition of the present embodiment and the cured product of the prepreg of the present embodiment. In addition, it can also be said that the printed wiring board of the present embodiment has one or more selected from the cured product of the thermosetting resin composition of the present embodiment, the cured product of the prepreg of the present embodiment and the laminate of the present embodiment.

[0156] The printed wiring board of the present embodiment can be manufactured, for example, by the following method: using one or more selected from the prepreg of the present embodiment, the resin film of the present embodiment and the laminate of the present embodiment, and performing circuit forming processing such as hole opening processing, metal plating processing, and etching based on metal foil by a known method. In addition, a multilayer bonding process can be further performed as needed to manufacture a multilayer printed wiring board. It should be noted that in the printed wiring board of the present embodiment, the prepreg of the present embodiment or the resin film of the present embodiment is C-staged to become a cured product.

[0157] [Antenna device]

[0158] The present disclosure also provides an antenna device having a laminate or printed wiring board of the present embodiment. The antenna device may be an antenna device having one laminate or a plurality of laminates or printed wiring boards. There is no particular limitation on the method of arranging the plurality of antenna elements, but for example, they are preferably arranged in a two-dimensional array. There is no particular limitation on the structure of the antenna device, and for example, reference may be made to Japanese Patent Gazette No. 6777273.

[0159] Considering the use as an antenna module, the laminate or printed wiring board in the antenna device preferably has conductor patterns such as a power supply conductor pattern, a ground conductor pattern, and a short-circuit conductor. The short-circuit conductor is a conductor that short-circuits the power supply conductor pattern and the ground conductor pattern, and is provided in a via portion described later.

[0160] The conductive pattern is preferably formed using a metal containing copper, aluminum, gold, silver, or an alloy thereof as a main component.

[0161] The laminated board or printed wiring board in the antenna device preferably has a via hole. The short-circuit conductor can be formed through the via hole, and the power supply conductor pattern and the ground conductor pattern can be electrically connected.

[0162] The method for forming the via hole is not particularly limited, and laser, plasma, or a combination thereof may be used. As the laser, a carbon dioxide laser, a YAG laser, a UV laser, an excimer laser, or the like may be used.

[0163] After the via is formed, a decontamination treatment using an oxidant may be performed. The oxidant is preferably a permanganate such as potassium permanganate or sodium permanganate; dichromate; ozone; hydrogen peroxide-sulfuric acid; nitric acid, more preferably a permanganate, and even more preferably a sodium hydroxide aqueous solution of a permanganate, or a so-called alkaline permanganic acid aqueous solution.

[0164] In addition, the laminated board or printed wiring board in the antenna device is preferably a laminated board or printed wiring board in which a short-circuit conductor is formed in the via hole after the via hole is formed. The conductor used here is preferably formed of the same metal as the metal forming the conductor pattern.

[0165] [Antenna module]

[0166] The present disclosure also provides an antenna module having a power supply circuit and the antenna device of the present embodiment. As the power supply circuit, although there is no particular limitation, an RFIC (Radio Frequency Integrated Circuit) or the like can be used. The RFIC has a switch, a power amplifier, a low noise amplifier, an attenuator, a phase shifter, a signal synthesizer-separator, a mixer, an amplifier circuit, etc.

[0167] The high-frequency signal supplied from the RFIC is transmitted to the feeding point of the power feeding conductor via the short-circuit conductor formed in the via hole of the antenna module laminate.

[0168] The structure of the antenna module is not particularly limited, but for example, Japanese Patent No. 6777273 can be referred to.

[0169] [communication device]

[0170] Furthermore, the present disclosure also provides a communication device including a baseband signal processing circuit and the antenna module of the present embodiment.

[0171] The communication device of this embodiment can upconvert the signal transmitted from the baseband signal processing circuit to the antenna module into a high-frequency signal and radiate it from the antenna device, and downconvert the high-frequency signal received by the antenna device and process the signal in the above-mentioned baseband signal processing circuit.

[0172] Although preferred embodiments have been described above, these are merely examples for explaining the present disclosure and are not intended to limit the scope of the present disclosure to these embodiments. The present disclosure also includes various forms different from the above embodiments without departing from the gist of the present disclosure.

[0173] Example

[0174] The present embodiment is described in detail below with reference to examples, but the present embodiment is not limited to the following examples.

[0175] In addition, in each example, the weight average molecular weight (Mw) was measured by the following method.

[0176] (Method for measuring weight average molecular weight (Mw))

[0177] The conversion was performed by gel permeation chromatography (GPC) based on a calibration curve using standard polystyrene. The calibration curve used standard polystyrene: TSK standard POLYSTYRENE (Type; A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) [manufactured by Tosoh Corporation, trade name], and was approximated by a cubic equation. The measurement conditions of GPC are shown below.

[0178] Device:

[0179] Pump: L-6200 model [manufactured by Hitachi High-Technologies Co., Ltd.]

[0180] Detector: L-3300 RI [manufactured by Hitachi High-Technologies Co., Ltd.]

[0181] Column oven: L-655A-52 [manufactured by Hitachi High-Technologies Co., Ltd.]

[0182] Column: Guard column; TSK Guardcolumn HHR-L + column; TSKgel G4000HHR + TSKgel G2000HHR (all manufactured by Tosoh Corporation, trade names)

[0183] Column size: 6.0×40mm (guard column), 7.8×300mm (column)

[0184] Eluent: Tetrahydrofuran

[0185] Sample concentration: 30mg / 5mL

[0186] Injection volume: 20 μL

[0187] Flow rate: 1.00mL / min

[0188] Measurement temperature: 40℃

[0189] In addition, about the (B) component and (E) component used in each example, the average particle diameter was measured by the following method.

[0190] (Method for measuring average particle size)

[0191] The particle size distribution was measured by a particle size distribution measuring device "MICROTRAC MT3300EXII" (manufactured by MICROTRAC BEL Co., Ltd.) to obtain the average particle size (d50). It should be noted that water (containing 0.1% by mass of sodium hexametaphosphate) was used as the measurement solvent, the measurement mode was set to permeation, and the measurement time was 30 seconds.

[0192] About the (C) component used in each example, the content ratio of the acidic group (acid anhydride group) was measured by the following method.

[0193] (Method for measuring the content ratio of acidic groups (acid anhydride groups))

[0194] 150 mL of acetone was added to 0.1 g of component (C), and 3 to 5 drops of phenolphthalein indicator were added to the solution dissolved at room temperature and mixed to prepare solution a. Separately, 3 to 5 drops of phenolphthalein indicator were added to 150 mL of acetone and mixed to prepare solution b.

[0195] Next, using an automatic titrator, solution a and solution b were titrated with 0.1 mol / L NaOH aqueous solution (titrant), and then titrated with 0.05 mol / L H2SO4 aqueous solution (titrant), and the content ratio of the acidic group (anhydride group) was calculated using the following mathematical formula (1).

[0196] mgKOH / g=(AB)C×56.1 / W(1)

[0197] A: Titration of acetone solution a in which component (C) is dissolved (mL)

[0198] B: Titration of acetone solution b (mL)

[0199] C: molar concentration of the titrant × valence of the acid or base

[0200] W: Weight of component (C) (g)

[0201] [Production Example 1: Production of modified maleimide compound (A-1)]

[0202] In a 2L reaction vessel equipped with a thermometer, a stirrer and a moisture meter with a reflux condenser, 15.6 g of a diamine-modified siloxane at both ends (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X-22-161B), 21.8 g of 3,3'-diethyl-4,4'-diaminodiphenylmethane, 274.2 g of 2,2-bis[4-(4-maleimidephenoxy)phenyl]propane and 200.0 g of propylene glycol monomethyl ether were added, and the mixture was reacted for 4 hours under reflux at 120° C. to obtain a solution of a modified maleimide compound (A-1). The weight average molecular weight (Mw) of the obtained modified maleimide compound (A-1) was 2500.

[0203] [Production Example 2: Production of modified maleimide compound (A-2)]

[0204] In a 2L reaction vessel equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser, which can be heated and cooled, 18.6 g of a diamine-modified siloxane at both ends (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X-22-161A), 21.8 g of 3,3'-diethyl-4,4'-diaminodiphenylmethane, 272.2 g of 2,2-bis[4-(4-maleimidephenoxy)phenyl]propane, and 200.0 g of propylene glycol monomethyl ether were added, and the mixture was reacted for 4 hours under reflux at 120° C. to obtain a solution of a modified maleimide compound (A-2). The weight average molecular weight (Mw) of the obtained modified maleimide compound (A-2) was 2700.

[0205] [Examples 1 to 14, Comparative Examples 1 to 4]

[0206] According to the formulation described in Table 1 or Table 2, the components described in Table 1 or Table 2 were stirred and mixed together with 58 parts by mass of toluene and 10 parts by mass of methyl isobutyl ketone at room temperature to prepare a thermosetting resin composition (varnish) having a solid content concentration of 60 to 65% by mass.

[0207] The varnish obtained in the above manner was applied to a glass cloth (E glass, manufactured by Nitto Bosho Co., Ltd.) having a thickness of 0.08 mm, and then heated and dried at 150° C. for 5 minutes to prepare a prepreg having a solid content of about 47% by mass from a thermosetting resin composition. A low-profile copper foil (BF-ANP18, Rz of the M surface: 1.5 μm, manufactured by CIRCUIT FOIL Co., Ltd.) having a thickness of 18 μm was arranged on the upper and lower sides of the prepreg in such a manner that the M surface (rough surface) was in contact with the prepreg, and then heated and pressed at a temperature of 230° C., a pressure of 3.0 MPa, and a time of 90 minutes to prepare a double-sided copper-clad laminate (thickness: 0.10 mm).

[0208] The double-sided copper-clad laminate obtained in each example was used to perform various evaluations according to the following methods.

[0209] [Evaluation of Double-Sided Copper Clad Laminates]

[0210] (1. Amount of outgassing (volatile gas) produced)

[0211] The outer copper foil of the double-sided copper-clad laminate obtained in each example was removed by immersion in a copper etching solution (a 10% by mass solution of ammonium persulfate, manufactured by Mitsubishi Gas Chemical Co., Ltd.), and a weight of 20 mg was weighed as a test piece, and the amount of outgassing (volatile gas) generated was measured by gas chromatography-mass spectrometry. The total area of ​​the obtained chart was calculated and used as the amount of outgassing. It should be noted that the analysis device used was a gas chromatograph-mass spectrometer "GC-MS QP-2010Plus" manufactured by Shimadzu Corporation.

[0212] The gas generation rate measured in this way must be within 12.0×10 7 Below, preferably 10.0×10 7 Below, more preferably 8.0×10 7 Below, more preferably 6.0×10 7 the following.

[0213] (2. Solder heat resistance)

[0214] The double-sided copper-clad laminate obtained in each example was cut into a square of 50 mm square, and the obtained test piece was floated in a solder bath at 288°C and allowed to stand for 300 seconds. The surface of the test piece was visually observed, and the time (unit: seconds) until the surface of the test piece expanded was measured. It should be noted that if no expansion occurred after standing for 300 seconds, it was recorded as ">300" in Table 1 or Table 2.

[0215] (3. Peel strength)

[0216] The copper foil of the double-sided copper foil resin plate obtained in each example was processed into a straight line with a width of 3 mm by etching, and then dried at 105° C. for 1 hour to prepare a test piece. Next, the copper foil of the test piece as a straight line was peeled off in a 90° direction at a speed of 50 mm / min using a small table tester (manufactured by Shimadzu Corporation, trade name: EZ-Test) to measure the peel strength.

[0217] (4. Relative dielectric constant (Dk) and dielectric loss tangent (Df))

[0218] The outer copper foil of the double-sided copper-clad laminate obtained in each example was removed by immersion in a copper etching solution (a 10% by mass solution of ammonium persulfate, manufactured by Mitsubishi Gas Chemical Co., Ltd.), and cut into a length of 60 mm and a width of 2 mm as a test piece, and the relative dielectric constant (Dk) and dielectric loss tangent (Df) were measured by the cavity resonator perturbation method. It should be noted that the measuring instrument used the vector network analyzer "N5227A" manufactured by Agilent Technologies, the cavity resonator used the "CP 129" (10 GHz band resonator) manufactured by Kanto Electronics Application Development Co., Ltd., and the measurement program used "CPMA-V2". In addition, the measurement was carried out under the conditions of a frequency of 10 GHz and a measurement temperature of 25°C.

[0219] [Table 1]

[0220] Table 1

[0221]

[0222] *1: Content relative to 100 parts by mass of the total resin components of the thermosetting resin composition

[0223] [Table 2]

[0224] Table 2

[0225]

[0226] *1: Content relative to 100 parts by mass of the total resin components of the thermosetting resin composition

[0227] Hereinafter, each component described in Table 1 and Table 2 will be described.

[0228] [(A) Thermosetting resin]

[0229] A-1: Modified maleimide compound (A-1) obtained in Production Example 1

[0230] A-2: Modified maleimide compound (A-2) obtained in Production Example 2

[0231] A-3: Naphthalene skeleton-containing epoxy resin "HP-9540" (manufactured by DIC Corporation)

[0232] ·A-4: Biphenyl aralkyl type epoxy resin "NC-3000-L" (manufactured by Nippon Kayaku Co., Ltd.)

[0233] A-5: Naphthalene skeleton-containing epoxy resin (naphthol novolac epoxy resin) "NC-7000-L" (manufactured by Nippon Kayaku Co., Ltd.)

[0234] A-6: Polyphenylene ether having methacryloyl groups at both ends of the molecule (weight average molecular weight 1700)

[0235] [(B) High dielectric constant inorganic filler]

[0236] B-1: Strontium titanate, average particle size (d50): 1.6 μm

[0237] B-2: calcium titanate, average particle size (d50): 2.1 μm

[0238] [(C) Resin having 3% by mass or more of acidic groups]

[0239] C-1: Copolymer resin of styrene and maleic anhydride, acid group (anhydride group) content ratio = 19 mass %, styrene / maleic anhydride (molar ratio) = 4, weight average molecular weight = 11000

[0240] C-2: Copolymer resin of styrene and maleic anhydride, acid group (anhydride group) content ratio = 10 mass %, styrene / maleic anhydride (molar ratio) = 8, weight average molecular weight = 14400

[0241] [(D) Elastomer: Styrene-based thermoplastic elastomer]

[0242] D-1: Maleic anhydride-modified hydrogenated styrene-based thermoplastic elastomer (maleic anhydride-modified SEBS), acid value 10 mg CH3ONa / g, styrene content 30% by mass

[0243] [(E) Inorganic filler]

[0244] E-1: Spherical fused silica: average particle size 1.5 μm, 50 mass% slurry (solvent: toluene)

[0245] [(F) Curing accelerator]

[0246] ·F-1: Isocyanate-masked imidazole compound

[0247] F-2: Dicyandiamide

[0248] [(G) Antioxidant]

[0249] ·G-1: 4,4'-butylenebis(6-tert-butyl-3-methylphenol)

[0250] [(H) Flame retardant]

[0251] ·H-1: Phosphate flame retardant

[0252] From the results in Tables 1 and 2, it can be seen that in Examples 1 to 14, the amount of outgassing is significantly reduced, the solder heat resistance is excellent, and the peel strength is high compared to Comparative Examples 1 to 4. In addition, a high relative dielectric constant (Dk) and a low dielectric loss tangent (Df) can be achieved, and it can be said that a laminate useful for antenna modules can be manufactured.

[0253] On the other hand, it can be seen that in Comparative Examples 1 to 4 in which the component (C) was not used, the amount of outgassing was large. In Comparative Examples 1 to 3, the peel strength was also reduced, and the peel strength of Comparative Example 4 was also insufficient. In particular, in Comparative Examples 3 and 4 in which the content of the antioxidant (G) was increased instead of the component (C), it was found that not only was the amount of outgassing not reduced, but the solder heat resistance was also reduced.

Claims

1. A thermosetting resin composition comprising: (A) a thermosetting resin, and (B) at least one high dielectric constant inorganic filler selected from titanium-based inorganic fillers and zirconium-based inorganic fillers, Furthermore, (C) a resin having 3% by mass or more of an acidic group is contained in an amount of 1 part by mass or more based on 100 parts by mass of the component (B).

2. The thermosetting resin composition according to claim 1, in, The acidic group contained in the component (C) is at least one selected from the group consisting of a carboxylic anhydride group, a carboxyl group, a sulfone group, and a phenolic hydroxyl group.

3. The thermosetting resin composition according to claim 1, in, The component (C) is a copolymer resin of an aromatic vinyl compound and maleic anhydride.

4. The thermosetting resin composition according to claim 1, in, The titanium-based inorganic filler is at least one selected from titanium dioxide and metal titanate.

5. The thermosetting resin composition according to claim 4, in, The metal titanate is at least one selected from alkali metal titanate, alkaline earth metal titanate and lead titanate.

6. The thermosetting resin composition according to claim 1, in, The zirconium-based inorganic filling material is an alkali metal zirconate.

7. The thermosetting resin composition according to claim 1, in, The content of the component (B) is 1% by volume to 60% by volume based on the total solid content in the thermosetting resin composition.

8. The thermosetting resin composition according to claim 1, in, The component (A) comprises at least one selected from epoxy resin, maleimide compound, modified polyphenylene ether resin, phenolic resin, polyimide resin, cyanate resin, isocyanate resin, benzoxazine resin, oxetane resin, amino resin, unsaturated polyester resin, allyl resin, dicyclopentadiene resin, silicone resin, triazine resin and melamine resin. 9 . A prepreg comprising the thermosetting resin composition according to claim 1 or a semi-cured product of the thermosetting resin composition. 10 . A resin film comprising the thermosetting resin composition according to claim 1 or a semi-cured product of the thermosetting resin composition. 11 . A laminate comprising a cured product of the thermosetting resin composition according to claim 1 or a cured product of the prepreg according to claim 9 , and a metal foil. 12 . A printed wiring board comprising at least one selected from the group consisting of a cured product of the thermosetting resin composition according to claim 1 and a cured product of the prepreg according to claim 9 . 13 . An antenna device comprising the laminated plate according to claim 11 . 14 . An antenna module comprising a power supply circuit and the antenna device according to claim 13 .

15. A communication device comprising a baseband signal processing circuit and the antenna module according to claim 14.

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