Resin compositions, resin-coated metal foils, prepregs, laminates, multilayer printed circuit boards, and semiconductor packages

Abstract

Provided is a resin composition containing a polyphenylene ether derivative (A) and a fluorine resin filler (B). Also provided are a metal foil with a resin, a prepreg, a layered board, a multilayered printed circuit board, and a semiconductor package, that include this resin composition.

Description

[Technical Field]

[0001] This disclosure relates to resin compositions, resin-coated metal foils, prepregs, laminates, multilayer printed circuit boards, and semiconductor packages. [Background technology]

[0002] Mobile communication devices such as mobile phones, their base station equipment, servers, routers and other network infrastructure equipment, and large computers are all experiencing increasing signal speeds and capacities year after year. Consequently, printed circuit boards (PCBs) used in these electronic devices require high-frequency compatibility, demanding substrate materials with excellent dielectric properties in the high-frequency band to reduce transmission loss. In recent years, in addition to the aforementioned electronic devices, new systems handling high-frequency wireless signals are being planned and implemented in the ITS (Intelligent Transport Systems) field (automotive and transportation systems) and in short-range indoor communications. Therefore, it is anticipated that low-transmission-loss substrate materials will be increasingly required for the PCBs used in these devices in the future.

[0003] Conventionally, polyphenylene ether (PPE) resins have been used as thermoplastic polymers with excellent high-frequency properties. For example, resin compositions containing polyphenylene ether and epoxy resin (see, for example, Patent Document 1), and resin compositions containing polyphenylene ether and cyanate resin (see, for example, Patent Document 2) are known. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 58-069046 [Patent Document 2] Special Publication No. 61-018937 [Overview of the project] [Problems that the invention aims to solve]

[0005] In recent years, there has been a strong demand for the development of resin compositions with improved dielectric properties (low dielectric constant and low dielectric loss tangent; hereinafter sometimes referred to as high-frequency properties) in the 10GHz band and above, which can be used in fifth-generation mobile communication system (5G) antennas that use radio waves in the frequency band above 6GHz and millimeter-wave radars that use radio waves in the frequency band of 30-300GHz. In other words, resin compositions are desired to have even better high-frequency properties than conventional ones. Furthermore, resin-coated metal foil, which has a layer of resin composition on a metal foil, is sometimes used in the manufacture of metal-clad laminates. This resin-coated metal foil is usually cut with a cutting machine to adjust the size. At this time, due to powder shedding from the edges of the resin-coated metal foil, resin powder may adhere to the cutting machine blade (hereinafter also referred to as the slit blade). This contamination of the slit blade can cause problems such as waviness and resin cracking at the cut surface, and contamination of the product by resin adhering to the slit blade falling onto the resin-coated metal foil.

[0006] In view of the current situation, this disclosure aims to provide a resin composition that exhibits excellent dielectric properties in the high frequency band of 10 GHz or higher, and that suppresses powder shedding at the edges when cutting resin-coated metal foil, as well as resin-coated metal foil, prepregs, laminates, multilayer printed circuit boards, and semiconductor packages using the resin composition. [Means for solving the problem]

[0007] As a result of diligent research to achieve the above objective, the present inventors have found that the above objective can be achieved by this disclosure.

[0008] This disclosure includes the following [1] to

[18] . [1] A resin composition containing a polyphenylene ether derivative (A) and a fluororesin filler (B). [2] The resin composition according to [1] above, wherein component (A) has an ethylenically unsaturated bond-containing group at the molecular terminus. [3] The resin composition according to [1] or [2] above, wherein the ethylenically unsaturated bond-containing group of component (A) is a (meth)acrylic group. [4] The resin composition according to any one of [1] to [3] above, wherein the weight-average molecular weight (Mw) of component (A) is 500 to 7,000. [5] The resin composition according to any one of [1] to [4] above, wherein component (B) is at least one selected from the group consisting of polytetrafluoroethylene (PTFE) filler, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA) filler, tetrafluoroethylene-hexafluoropropylene copolymer (FEP) filler, tetrafluoroethylene-ethylene copolymer (ETFE) filler, and polychlorotrifluoroethylene (PCTFE) filler. [6] The resin composition according to any one of [1] to [5] above, wherein the average particle size of component (B) is 0.1 to 10 μm. [7] The resin composition according to any one of [1] to [6] above, wherein the content of component (B) is 1% by mass or more and less than 50% by mass with respect to the solid content of the resin composition. [8] The resin composition according to any one of [1] to [7] above, wherein the content of component (B) is 1 to 40% by mass relative to the solid content of the resin composition. [9] The resin composition according to any one of [1] to [8] above, further comprising one or more thermosetting resins (C) selected from the group consisting of epoxy resins, cyanate resins, and maleimide compounds.

[10] The resin composition according to [9] above, wherein the (C) component contains the maleimide compound, and the maleimide compound is a modified maleimide compound having a structural unit derived from a maleimide compound (c1) having at least two N-substituted maleimide groups and a structural unit derived from an amine compound (c2) having a primary amino group.

[11] The resin composition according to

[10] above, wherein the modified maleimide compound is a compound represented by the following general formula (C-1). [ka] (In the formula, X c1 and X c2 These are each independently divalent organic groups.

[12] The resin composition according to any one of [9] to

[11] above, wherein the content ratio of component (A) to component (C) [(A) / (C)] is 5 / 95 to 80 / 20 by mass ratio.

[13] The resin composition according to any one of [1] to

[12] above, further comprising one or more selected from the group consisting of thermoplastic elastomer (D), curing accelerator (E), and inorganic filler (F).

[14] A resin-coated metal foil having a layer of the resin composition described in any of [1] to

[13] above on the metal foil.

[15] A prepreg comprising the resin composition described in any of [1] to

[13] above and a sheet-like fiber-reinforced substrate.

[16] A laminate containing (i) the resin-coated metal foil described in

[14] above, or (ii) the prepreg and metal foil described in

[15] above.

[17] A multilayer printed circuit board comprising (i) a resin-coated metal foil as described in

[14] above, (ii) a prepreg as described in

[15] above, or (iii) a laminate as described in

[16] above.

[18] A semiconductor package comprising the multilayer printed circuit board described in

[17] above and a semiconductor element. [Effects of the Invention]

[0009] This disclosure makes it possible to provide a resin composition that exhibits excellent dielectric properties in high frequency bands of 10 GHz or higher and suppresses powder shedding at the edges when cutting resin-coated metal foil, as well as resin-coated metal foil, prepregs, laminates, multilayer printed circuit boards, and semiconductor packages using the resin composition. [Brief explanation of the drawing]

[0010] [Figure 1] This is a photograph of the slit blade of the cutting machine used to evaluate edge powder shedding during resin-coated copper foil cutting in the examples and comparative examples. [Figure 2]This is a schematic diagram showing the appearance of the slit blade when the evaluation of edge powder shedding during resin-coated copper foil cutting is "A" in the examples and comparative examples. [Figure 3] This is a schematic diagram showing the appearance of the slitting blade when the evaluation of edge powder shedding during resin-coated copper foil cutting is "C" in the examples and comparative examples. [Modes for carrying out the invention]

[0011] In the numerical ranges described herein, the upper or lower limits of those ranges may be replaced with the values ​​shown in the examples. Furthermore, the lower and upper limits of a numerical range can be arbitrarily combined with the lower or upper limits of other numerical ranges. In the notation "AA~BB" for a numerical range, the numbers AA and BB at both ends are included in the range as the lower and upper limits, respectively. Furthermore, 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 composition means the total amount of multiple substances present in the composition, unless otherwise specified, if multiple substances corresponding to each component are present in the composition. This disclosure and these embodiments also include any combination of the information described herein. In this embodiment, "resin components" are defined as all components of the resin composition that are made up of solid matter, excluding inorganic compounds such as inorganic fillers described later, as well as flame retardants and flame retardant enhancers. Furthermore, in this embodiment, the term "solid content" refers to components in the resin composition other than water and volatile substances such as solvents described later. In other words, the solid content includes liquid, syrup-like, or waxy substances at room temperature around 25°C, and does not necessarily mean that the substance is solid.

[0012] [Resin composition] The resin composition of this embodiment is a resin composition containing a polyphenylene ether derivative (A) [hereinafter sometimes abbreviated as "component (A)"] and a fluororesin filler (B) [hereinafter sometimes abbreviated as "component (B)"]. The resin composition of this embodiment is preferably a thermosetting resin composition. In the resin composition of this embodiment, the total content of component (A) and component (B) is preferably 15% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass, relative to the solid content of the resin composition. There is no particular upper limit to the total content of component (A) and component (B), and it may be 100% by mass, 90% by mass or less, 80% by mass or less, or 65% by mass or less, relative to the solid content of the resin composition. The following describes each component contained in the resin composition of this embodiment.

[0013] <Polyphenylene ether derivative (A)> The polyphenylene ether derivative (A) is not particularly limited, and known polyphenylene ether derivatives, such as those having a structural unit represented by the general formula (A-2) described later, can be used. In particular, from the viewpoint of high-frequency characteristics and compatibility with the thermosetting resin (C) and thermoplastic elastomer (D) used as needed, the polyphenylene ether derivative (A) is preferably a polyphenylene ether derivative having an ethylenically unsaturated bond-containing group at the molecular terminal, and more preferably a polyphenylene ether derivative having ethylenically unsaturated bond-containing groups at both ends of the molecule. In this specification, "ethylenically unsaturated bond-containing group" means a substituent containing a carbon-carbon double bond that can undergo addition reactions, and does not include double bonds in aromatic rings. Polyphenylene ether derivative (A) may be used alone or in combination of two or more types.

[0014] Examples of the ethylenically unsaturated bond-containing groups include unsaturated aliphatic hydrocarbon groups such as vinyl groups, allyl groups, 1-methylallyl groups, isopropenyl groups, 2-butenyl groups, 3-butenyl groups, and styryl groups; maleimide groups; and groups containing heteroatoms and ethylenically unsaturated bonds, such as the group represented by the following general formula (A-1). Among these, the group represented by the following general formula (A-1) is preferred from the viewpoint of high-frequency characteristics and adhesion to conductors.

[0015] [ka] (In the formula, R a1 * represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. * indicates the bond position.

[0016] R a1 The alkyl group having 1 to 20 carbon atoms represented by may be a linear alkyl group, a branched alkyl group, or a cyclic alkyl group, and a linear alkyl group is preferred. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, and particularly preferably 1. Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, pentadecyl, hexadecyl, and heptadecyl groups, and among these, the methyl group is preferred. The group represented by the above general formula (A-1) is a (meth)acrylic group [that is, R in the above general formula (A-1)], from the viewpoint of high-frequency characteristics and adhesion to conductors. a1 However, it is preferable that the group is a hydrogen atom or a methyl group, and more preferably a methacrylic group. In this embodiment, "(meth)acrylic group" means an acrylic group or a methacrylic group.

[0017] In this specification, groups that have a portion of an unsaturated aliphatic hydrocarbon group, such as a maleimide group or the group represented by the general formula (A-1) above, but cannot be considered an unsaturated aliphatic hydrocarbon group when viewed as a whole, are not included in the above-mentioned "unsaturated aliphatic hydrocarbon group".

[0018] The number of ethylenically unsaturated bond-containing groups in one molecule of the polyphenylene ether derivative (A) is not particularly limited, but is preferably 2 to 5, more preferably 2 to 3, and even more preferably 2. When the number of ethylenically unsaturated bond-containing groups is above the lower limit, excellent high-frequency properties and good compatibility with the thermosetting resin (C) and thermoplastic elastomer (D) described later tend to be obtained. On the other hand, when the number of ethylenically unsaturated bond-containing groups is below the upper limit, excellent fluidity and moldability tend to be obtained. As described above, the polyphenylene ether derivative (A) preferably has an ethylenically unsaturated bond-containing group at its molecular terminus, and may also have ethylenically unsaturated bond-containing groups in other locations besides the molecular terminus, but it is more preferable that it has ethylenically unsaturated bond-containing groups only at the molecular terminus. The polyphenylene ether derivative (A) is preferably a polyphenylene ether having a methacrylic group at its molecular terminus, and more preferably a polyphenylene ether having methacrylic groups at both ends of the molecule. The methacrylic group may be bonded to an oxygen atom, that is, it may be a methacryloyloxy group.

[0019] The polyphenylene ether derivative (A) has a phenylene ether bond and preferably has a structural unit represented by the following general formula (A-2).

[0020] [ka] (In the formula, R a2 This represents an aliphatic hydrocarbon group or halogen atom having 1 to 5 carbon atoms. a1 (This represents an integer between 0 and 4.)

[0021] R in the general formula (A-2) above a2 Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by a2 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, and the like. As the aliphatic hydrocarbon group, an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group is even more preferable. n a1 represents an integer of 0 to 4, 1 or 2 is preferable, and 2 is more preferable. Note that n a1 When is 1 or 2, R a2 is preferably substituted at the ortho position on the benzene ring (however, based on the substitution position of the oxygen atom). Also, when n a1 is an integer of 2 or more, a plurality of Rs a2 may be the same or different from each other. The structural unit represented by the general formula (A-2) is preferably a structural unit represented by the following general formula (A-2').

[0022]

Chemical formula

[0023] From the viewpoints of high-frequency characteristics and adhesion to a conductor, the polyphenylene ether derivative (A) is preferably a compound represented by the following general formula (A-3).

[0024]

Chemical formula

[0025] In the above general formula (A-3), R a3 and R a4 The explanation for the aliphatic hydrocarbon group with 1 to 5 carbon atoms shown is as follows: a2 This is the same as the explanation for aliphatic hydrocarbon groups with 1 to 5 carbon atoms shown. n a2 and n a3 n represents an integer between 0 and 4, preferably between 0 and 3, and preferably 2 or 3. a2 If is an integer greater than or equal to 2, then multiple R a3 The elements may be identical or different. a3 If is an integer greater than or equal to 2, then multiple R a4 They may be the same or they may be different. n a4 and n a5 n represents an integer between 0 and 20, preferably between 1 and 20, more preferably between 2 and 15, and even more preferably between 3 and 10. a4 or n a5 If n is an integer greater than or equal to 2, then multiple n a1 They may be the same or they may be different. n a4 and n a5 The sum of the integers is an integer between 1 and 30, preferably between 2 and 25, more preferably between 5 and 20, and even more preferably between 7 and 15.

[0026] X in the above general formula (A-3) a1Examples of alkylene groups having 1 to 5 carbon atoms include methylene group, 1,2-dimethylene group, 1,3-trimethylene group, 1,4-tetramethylene group, and 1,5-pentamethylene group. X a1 Examples of alkylidene groups having 2 to 5 carbon atoms include ethylidene, propyridene, isopropylidene, butylidene, isobutylidene, pentylidene, and isopentylidene. X a1 Among the groups shown, the isopropylidene group is preferred from the viewpoint of high-frequency characteristics and adhesion to conductors. Y a1 and Y a2 The preferred embodiment of the ethylenically unsaturated bond-containing group shown is as described above. From the viewpoint of high-frequency characteristics and adhesion to conductors, the compound represented by the above general formula (A-3) is preferably the compound represented by the following general formula (A-4).

[0027] [ka] (In the formula, n a4 and n a5 This is as explained in the general formula (A-3) above. a5 and R a6 Each of these independently represents either a hydrogen atom or a methyl group. a2 (This indicates a methylene group or an isopropylidene group.)

[0028] [Weight-average molecular weight (Mw) of polyphenylene ether derivative (A)] The weight-average molecular weight (Mw) of the polyphenylene ether derivative (A) is not particularly limited, but is preferably 500 to 7,000, more preferably 800 to 5,000, even more preferably 1,000 to 3,000, and particularly preferably 1,200 to 2,500. When the weight-average molecular weight (Mw) of component (A) is above the lower limit, a cured product with excellent dielectric properties and heat resistance tends to be obtained. When the weight-average molecular weight (Mw) of component (A) is below the upper limit, excellent moldability tends to be obtained. In this specification, the weight-average molecular weight is a value calculated from a calibration curve using standard polystyrene by gel permeation chromatography (GPC), and more specifically, a value obtained by the measurement method described in the examples.

[0029] The method for synthesizing the polyphenylene ether derivative (A) is not particularly limited and can be any known method for synthesizing or modifying polyphenylene ethers.

[0030] (Content of component (A)) The content of polyphenylene ether derivative (A) in the resin composition of this embodiment is not particularly limited, but is preferably 1 to 80 parts by mass, more preferably 1 to 45 parts by mass, even more preferably 1 to 20 parts by mass, and particularly preferably 2 to 10 parts by mass, per 100 parts by mass of the total resin components. When the content of component (A) is above the lower limit, there is a tendency to obtain better high-frequency characteristics and low hygroscopicity. When the content of component (A) is below the upper limit, there is a tendency to obtain better heat resistance, moldability, and processability.

[0031] <Fluororesin filler (B)> The resin composition of this embodiment, by containing a fluororesin filler (B), provides excellent high-frequency characteristics and effectively suppresses powder shedding at the edges when cutting the resin-coated metal foil. This effect is particularly pronounced when components (A) and (B) are combined. Including a fluororesin filler (B) in the resin composition results in a greater improvement in high-frequency characteristics and a greater suppression of powder shedding at the edges when cutting the resin-coated metal foil compared to simply including fluororesin itself. Examples of the shape of the fluororesin filler (B) include particulate, powdery, needle-shaped, columnar, plate-shaped, and flake-shaped. Among these, particulate is preferred. The fluororesin filler (B) may be a slurry mixed with an organic solvent. Examples of the organic solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone (MIBK), cyclohexanone, and other ketone compounds. Fluoropolymer filler (B) may be used alone or in combination of two or more types.

[0032] Examples of fluororesin fillers (B) include polytetrafluoroethylene (PTFE) fillers, tetrafluoroethylene-perfluoroalkyl vinyl ether (PFA) fillers, tetrafluoroethylene-hexafluoropropylene (FEP) fillers, tetrafluoroethylene-ethylene copolymer (ETFE) fillers, and polychlorotrifluoroethylene (PCTFE) fillers. Among these, PTFE fillers are preferred as fluororesin fillers (B) from the viewpoint of high-frequency characteristics and suppression of powder shedding at the edges when cutting the resin-coated metal foil. The surface of the fluororesin filler (B) may also be coated with an inorganic filler. The average particle size of the fluororesin filler (B) is preferably 0.1 to 10 μm, more preferably 0.2 to 5 μm, even more preferably 0.5 to 4.0 μm, and particularly preferably 1.5 to 4.0 μm. Here, the average particle size can be calculated, for example, by laser diffraction particle size distribution measurement, and the same applies hereafter.

[0033] (Content of component (B)) The content of fluororesin filler (B) is preferably 1% by mass or more and less than 50% by mass, more preferably 1 to 45% by mass, even more preferably 1 to 40% by mass, and particularly preferably 5 to 40% by mass, relative to the solid content of the resin composition, and may also be 15 to 40% by mass or 25 to 40% by mass. If the content of fluororesin filler (B) is 1% by mass or more relative to the solid content of the resin composition, sufficient high-frequency characteristics tend to be obtained. On the other hand, if the content of fluororesin filler (B) is less than 50% by mass relative to the solid content of the resin composition, a decrease in adhesion between the metal foil and the organic components in the resin composition can be suppressed, and a decrease in heat resistance and copper foil peel strength tends to be avoided.

[0034] When using fluororesin filler (B), a coupling agent may be used in combination as needed to improve the dispersibility of fluororesin filler (B) and the adhesion between fluororesin filler (B) and organic components in the resin composition. Examples of coupling agents include silane coupling agents and titanate coupling agents. One type of coupling agent may be used alone, or two or more types may be used in combination. When using a coupling agent, the processing method may be a so-called integral blending method, in which the fluororesin filler (B) is blended into the resin composition and then the coupling agent is added. However, it is preferable to use an inorganic filler that has been surface-treated with the coupling agent beforehand, either dry or wet. By adopting the latter method, the characteristics of the fluororesin filler (B) can be expressed more effectively. Furthermore, the fluororesin filler (B) may be used as a slurry that has been pre-dispersed in an organic solvent, if necessary.

[0035] <Thermosetting resin (C)> The resin composition of this embodiment preferably further contains one or more thermosetting resins (C) selected from the group consisting of epoxy resins, cyanate resins, and maleimide compounds. Among these, from the viewpoint of high-frequency characteristics, insulation reliability, adhesion to conductors, and flame retardancy, the thermosetting resin (C) preferably contains a maleimide compound. The thermosetting resin (C) may be used alone or in combination of two or more types.

[0036] (Epoxy resin) The epoxy resin is preferably one having two or more epoxy groups in one molecule. Here, epoxy resins are classified into glycidyl ether type epoxy resins, glycidyl amine type epoxy resins, glycidyl ester type epoxy resins, etc. Among these, glycidyl ether type epoxy resins are preferred. Epoxy resins are classified into various types based on differences in their main skeleton. Within each of the above types of epoxy resins, they are further classified into bisphenol-type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin; alicyclic epoxy resins such as dicyclopentadiene type epoxy resin; aliphatic chain epoxy resins; novolac-type 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 type epoxy resin; xylylene type epoxy resin; and dihydroanthracene type epoxy resin. When using epoxy resin, a hardener, curing aid, etc., may be used in combination as needed.

[0037] (Cyanate resin) Examples of cyanate resins include 2,2-bis(4-cyanatophenyl)propane, bis(4-cyanatophenyl)ethane, bis(3,5-dimethyl-4-cyanatophenyl)methane, 2,2-bis(4-cyanatophenyl)-1,1,1,3,3,3-hexafluoropropane, α,α'-bis(4-cyanatophenyl)-m-diisopropylbenzene, cyanate ester compounds of phenol-added dicyclopentadiene polymers, phenol novolac type cyanate ester compounds, and cresol novolac type cyanate ester compounds. When using cyanate resin, a curing agent, curing aid, etc. for the cyanate resin may be used in combination as needed.

[0038] (Maleimide compounds) The maleimide compound is preferably one or more selected from the group consisting of maleimide compounds (c1) having two or more N-substituted maleimide groups [hereinafter sometimes simply referred to as "maleimide compound (c1)" or "component (c1)"] and its derivatives. The above-mentioned "derivatives" include addition reaction products of a maleimide compound having two or more N-substituted maleimide groups and an amine compound such as a diamine compound, which will be described later.

[0039] The maleimide compound (c1) is not particularly limited as long as it is a maleimide compound having two or more N-substituted maleimide groups. Specific examples of the maleimide compound (c1) include aromatic maleimide compounds such as bis(4-maleimidophenyl)methane, polyphenylmethanemaleimide, bis(4-maleimidophenyl)ether, bis(4-maleimidophenyl)sulfone, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, m-phenylenebismaleimide, and 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane; and aliphatic maleimide compounds such as 1,6-bismaleimide-(2,2,4-trimethyl)hexane and pyrrolironate binder-type long-chain alkylbismaleimide. Among these, from the viewpoint of adhesion to conductors and mechanical properties, aromatic maleimide compounds are preferred as maleimide compounds (c1), aromatic bismaleimide compounds are more preferred, and 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane and 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide are even more preferred.

[0040] As the maleimide compound (c1), a compound represented by the following general formula (C1-1) is preferred.

[0041] [ka] (In the formula, X c1 (This indicates a divalent organic group.)

[0042] X in the above general formula (C1-1) c1 Examples of divalent organic groups shown include those represented by the following general formulas (C1-2), (C1-3), (C1-4), or (C1-5).

[0043] [ka] (In the formula, R c1This represents an aliphatic hydrocarbon group or halogen atom having 1 to 5 carbon atoms. c1 The asterisk (*) indicates an integer between 0 and 4.

[0044] R c1 Examples of aliphatic hydrocarbon groups having 1 to 5 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, and n-pentyl groups. Aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferred, with the methyl group being more preferred. n c1 n represents an integer between 0 and 4, and from the viewpoint of availability, an integer between 0 and 2 is preferred, and 0 is more preferred. c1 If is an integer greater than or equal to 2, then multiple R c1 They may be the same or they may be different.

[0045] [ka] (In the formula, R c2 and R c3 Each of these independently represents an aliphatic hydrocarbon group or halogen atom having 1 to 5 carbon atoms. c2 n represents 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 (C1-3-1). c2 and n c3 Each of these independently represents an integer between 0 and 4. * indicates the join position.

[0046] R c2 and R c3 The explanation for the aliphatic hydrocarbon group with 1 to 5 carbon atoms shown is as follows: R in the general formula (C1-2) above. c1 This is the same as the explanation for aliphatic hydrocarbon groups with 1 to 5 carbon atoms shown. X c2Examples 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. A alkylene group having 1 to 3 carbon atoms is preferred, and a methylene group is more preferred. X c2 Examples of alkylidene groups having 2 to 5 carbon atoms include ethylidene, propyridene, isopropylidene, butyridene, isobutylidene, pentylidene, and isopentylidene. Isopropylidene is preferred as the alkylidene group. n c2 and n c3 n represents an integer between 0 and 4, and from the viewpoint of availability, an integer between 0 and 2 is preferred, with 0 or 2 being more preferred. c2 If is an integer greater than or equal to 2, then multiple R c2 The elements may be identical or different. c3 If is an integer greater than or equal to 2, then multiple R c3 They may be the same or they may be different. X c2 The divalent group represented by the general formula (C1-3-1) is as follows:

[0047] [ka] (In the formula, R c4 and R c5 Each of these independently represents an aliphatic hydrocarbon group or halogen atom having 1 to 5 carbon atoms. c3 This represents 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. c4 and n c5 Each of these independently represents an integer between 0 and 4. * indicates the join position.

[0048] R c4 and R c5The description of the aliphatic hydrocarbon group having 1 to 5 carbon atoms shown by c1 is the same as the description of the aliphatic hydrocarbon group having 1 to 5 carbon atoms shown by X c3 As the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms shown by c2 X in the general formula (C1-3) includes the same alkylene group having 1 to 5 carbon atoms and alkylidene group having 2 to 5 carbon atoms. Among these, from the viewpoints of high-frequency characteristics, adhesion to a conductor, heat resistance, glass transition temperature, and thermal expansion coefficient, an isopropylidene group is preferred. X c3 Among the groups shown by n c4 and n c5 represent an integer of 0 to 4, and from the viewpoint of easy availability, an integer of 0 to 2 is preferred, and 0 is more preferred. When n c4 is an integer of 2 or more, a plurality of R c4 may be the same as or different from each other. When n c5 is an integer of 2 or more, a plurality of R c5 may be the same as or different from each other.

[0049]

Chemical formula

[0050] n c6 From the viewpoint of easy availability, an integer of 1 to 5 is preferred, and an integer of 1 to 3 is more preferred.

[0051]

Chemical formula

[0052] R c6 and R c7 The explanation for the aliphatic hydrocarbon group with 1 to 5 carbon atoms shown is as follows: R in the general formula (C1-2) above. c1 This is the same as the explanation for aliphatic hydrocarbon groups with 1 to 5 carbon atoms shown. n c7 represents an integer from 1 to 8, preferably an integer from 1 to 3, and more preferably 1. n c7 If is an integer greater than or equal to 2, then multiple R c6 They may be the same or different, and multiple Rs c7 They may be the same or they may be different.

[0053] X in the above general formula (C1-1) c1 From the perspective of high-frequency characteristics, the following equation (X c1 -1)~(X c1 It is preferably a divalent group represented by any of the following formulas (X c1 It is more preferable that the group is a divalent group represented by (-3).

[0054] [ka] (In the formula, * indicates the bond position with the nitrogen atom in the maleimide group.)

[0055] As the maleimide compound, a derivative of maleimide compound (c1) is preferred from the viewpoint of solubility in organic solvents, compatibility, adhesion to conductors, and high-frequency characteristics. Preferably, the derivative of maleimide compound (c1) is a modified maleimide compound (X) [hereinafter sometimes abbreviated as "modified maleimide compound (X)" or "(X) component"] having a structural unit derived from maleimide compound (c1) and a structural unit derived from an amine compound (c2) having a primary amino group [hereinafter sometimes abbreviated as "amine compound (c2)" or "(c2) component"]. In other words, the resin composition of this embodiment preferably contains the maleimide compound as component (C), and the maleimide compound is a modified maleimide compound having a structural unit derived from a maleimide compound (c1) having at least two N-substituted maleimide groups and a structural unit derived from an amine compound (c2) having a primary amino group. Furthermore, the structural units derived from component (c1) and component (c2) contained in the modified maleimide compound (X) may be one type each, or a combination of two or more types.

[0056] The modified maleimide compound (X) is preferably a compound containing a structure represented by the following formula (C-1), which is formed by an addition reaction between the maleimide group of component (c1) and the primary amino group of component (c2). [ka] (* indicates the location of binding to other structures.)

[0057] (c1) Structural units derived from component include, for example, one or more selected from the group consisting of groups represented by the following general formula (C1-6) and groups represented by the following general formula (C1-7).

[0058] [ka] (In the formula, X c1 X in the above general formula (C1-1) is c1 (This is equivalent to the above, and * indicates the binding site to other structures.)

[0059] The content of structural units derived from component (c1) in the modified maleimide compound (X) is not particularly limited, but is preferably 50 to 95% by mass, more preferably 70 to 92% by mass, and even more preferably 85 to 90% by mass. When the content of structural units derived from component (c1) is within the above range, the high-frequency characteristics tend to be better and good film handling properties tend to be obtained.

[0060] The amine compound (c2) is preferably a compound having two or more amino groups, and more preferably a diamine compound having two amino groups. Examples of amine compounds (c2) include 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 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'-[1,3-phenylenebis(1-methylethylidene)]bisaniline Examples include aromatic diamine compounds such as 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; and amine-modified siloxane compounds having a primary amino group.

[0061] Among these, 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 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 component (c2) from the viewpoint of excellent solubility in organic solvents, reactivity with component (c1), and heat resistance. Furthermore, 3,3'-dimethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane is preferred as component (c2) from the viewpoint of excellent high-frequency properties and low water absorption. Furthermore, from the viewpoint of excellent mechanical properties such as adhesion to conductors, elongation, and tensile strength, 2,2-bis[4-(4-aminophenoxy)phenyl]propane is preferred as component (c2). In addition, from the viewpoint of excellent solubility in organic solvents, reactivity during synthesis, heat resistance, and adhesion to conductors, as well as excellent high-frequency characteristics and low hygroscopicity, 4,4'-[1,3-phenylenebis(1-methylethylidene)]bisaniline and 4,4'-[1,4-phenylenebis(1-methylethylidene)]bisaniline are preferred as component (c2).

[0062] As the amine compound (c2), a compound represented by the following general formula (C2-1) is preferred.

[0063] [ka] (In the formula, X c4 (This indicates a divalent organic group.)

[0064] The (c2) component is X in the above general formula (C2-1). c4 However, it is preferable to contain an aromatic diamine compound, which is a divalent group represented by the following general formula (C2-2) [hereinafter sometimes abbreviated as "aromatic diamine compound (C2-2)"].

[0065] [ka] (In the formula, R c11 and R c12 Each of these independently represents 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. c5 This refers to an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, a fluorenylene group, a single bond, or a divalent group represented by the following general formulas (C2-2-1) or (C2-2-2). c8 and n c9 Each of these independently represents an integer between 0 and 4. * indicates the join position.

[0066] In the above general formula (C2-2), R c11 and R c12 Examples of aliphatic hydrocarbon groups having 1 to 5 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, and n-pentyl groups. X c5 Examples of alkylene groups having 1 to 5 carbon atoms include methylene group, 1,2-dimethylene group, 1,3-trimethylene group, 1,4-tetramethylene group, and 1,5-pentamethylene group. X c5 Examples of alkylidene groups having 2 to 5 carbon atoms include ethylidene, propyridene, isopropylidene, butylidene, isobutylidene, pentylidene, and isopentylidene. n c8 and n c9 n represents an integer between 0 and 4, and from the viewpoint of availability, 0 or 1 is preferred. c8 or n c9 If is an integer greater than or equal to 2, then multiple R c11 Each or multiple R c12 They may be the same or they may be different. X in the above general formula (C2-2) c5 The divalent group represented by the general formula (C2-2-1) is as follows:

[0067] [ka] (In the formula, R c13 and R c14 Each of these independently represents an aliphatic hydrocarbon group or halogen atom having 1 to 5 carbon atoms. c6 n represents 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. c10 and n c11 Each of these independently represents an integer between 0 and 4. * indicates the join position.

[0068] In the above general formula (C2-2-1), R c13 and R c14 The explanation for the aliphatic hydrocarbon group with 1 to 5 carbon atoms shown is as follows: R in the general formula (C2-2) above. c11 and R c12 This is the same as the explanation for aliphatic hydrocarbon groups with 1 to 5 carbon atoms shown. X c6 The explanation for alkylene groups with 1 to 5 carbon atoms and alkylidene groups with 2 to 5 carbon atoms shown is given by X in the general formula (C2-2) above. c5 This is the same as the explanation given for alkylene groups with 1 to 5 carbon atoms and alkylidene groups with 2 to 5 carbon atoms. n c10 and n c11 n represents an integer between 0 and 4, and from the viewpoint of availability, an integer between 0 and 2 is preferred, and 0 is more preferred. c10 If is an integer greater than or equal to 2, then multiple R c13 The elements may be identical or different. c11 If is an integer greater than or equal to 2, then multiple R c14 They may be the same or they may be different. X in the above general formula (C2-2) c5 The divalent group represented by the general formula (C2-2-2) is as follows:

[0069] [ka] (In the formula, R c15 X represents an aliphatic hydrocarbon group or halogen atom having 1 to 5 carbon atoms. c7 and X c8 Each of these independently represents an alkylene group with 1 to 5 carbon atoms, an alkylidene group with 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, or a single bond. c12 The asterisk (*) indicates an integer between 0 and 4.

[0070] In the above general formula (C2-2-2), R c15 The explanation for the aliphatic hydrocarbon group with 1 to 5 carbon atoms shown is as follows: R in the general formula (C2-2) above. c11 and R c12 This is the same as the explanation for aliphatic hydrocarbon groups with 1 to 5 carbon atoms shown. X c7 and X c8 The alkylene group with 1 to 5 carbon atoms and the alkylidene group with 2 to 5 carbon atoms shown are X in the general formula (C2-2) above. c5 Examples include alkylene groups with 1 to 5 carbon atoms and alkylidene groups with 2 to 5 carbon atoms, as indicated by [the symbol]. Among these, X c7 and X c8 Preferably, it is an alkylidene group having 2 to 5 carbon atoms, and more preferably an ilopropylidene group. n c12 n represents an integer between 0 and 4, and from the viewpoint of availability, an integer between 0 and 2 is preferred, and 0 is more preferred. c12 If is an integer greater than or equal to 2, then multiple R c15 They may be the same or they may be different.

[0071] Furthermore, the (c2) component is X in the general formula (C2-1) above. c4 However, it may also contain an amine-modified siloxane compound which is a divalent group containing a structural unit represented by the following general formula (C2-3), and X in the above general formula (C2-1) c4However, it may also contain a terminal amine-modified siloxane compound, which is a divalent group represented by the following general formula (C2-4) [hereinafter sometimes abbreviated as "terminal amine-modified siloxane compound (C2-4)"].

[0072] [ka] (In the formula, R c16 and R c17 Each of these independently represents an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a substituted phenyl group. * indicates the bond position.

[0073] [ka] (In the formula, R c16 and R c17 This is the same as the one in the general formula (C2-3) above, and R c18 and R c19 Each of these independently represents an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a substituted phenyl group. c9 and X c10 Each independently represents a divalent organic group, n c13 (The asterisk (*) indicates an integer between 2 and 100.)

[0074] In the above general formulas (C2-3) and (C2-4), R c16 ~R c19 Examples of C1-C5 alkyl groups represented by include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, and n-pentyl groups. C1-C3 alkyl groups are preferred, and methyl groups are more preferred. R c16 ~R c19Examples of substituents on the phenyl group in the substituted phenyl group shown include C1-C5 alkyl groups, C2-C5 alkenyl groups, and C2-C5 alkynyl groups. Examples of C1-C5 alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, and n-pentyl groups. Examples of C2-C5 alkenyl groups include vinyl and allyl groups. Examples of C2-C5 alkynyl groups include ethynyl and propargyl groups. X c9 and X c10 Examples of divalent organic groups include alkylene groups, alkenylene groups, alkylene groups, arylene groups, -O- groups, or divalent linking groups formed by combinations thereof. Examples of alkylene groups include alkylene groups having 1 to 10 carbon atoms, such as methylene groups, ethylene groups, and propylene groups. Examples of alkenylene groups include alkenylene groups having 2 to 10 carbon atoms. Examples of alkylene groups include alkylene groups having 2 to 10 carbon atoms. Examples of arylene groups include arylene groups having 6 to 20 carbon atoms, such as phenylene groups and naphthylene groups. Among these, X c9 and X c10 Of these, alkylene groups and arylene groups are preferred, with alkylene groups being more preferred. n c13 n represents 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. c13 If is an integer greater than or equal to 2, then multiple R c16 Each or multiple R c17 They may be the same or they may be different.

[0075] (c2) Structural units derived from component (c2) include, for example, one or more selected from the group consisting of the group represented by the following general formula (C2-5) and the group represented by the following general formula (C2-6). [ka] (In the formula, X c4 X in the above general formula (C2-1) is c4 (This is equivalent to the above, and * indicates the binding site to other structures.)

[0076] The content of structural units derived from component (c2) in the modified maleimide compound (X) is not particularly limited, but is preferably 5 to 50% by mass, more preferably 8 to 30% by mass, and even more preferably 10 to 15% by mass. When the content of structural units derived from component (c2) is within the above range, excellent high-frequency properties and better heat resistance, flame retardancy, and glass transition temperature tend to be obtained.

[0077] The total content of structural units derived from component (c1) and component (c2) in the modified maleimide compound (X) is not particularly limited, but is preferably 80% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and particularly preferably 100% by mass (i.e., consisting only of structural units derived from component (c1) and component (c2)).

[0078] The ratio of structural units derived from component (c1) to structural units derived from component (c2) in the modified maleimide compound (X) is not particularly limited, but the ratio (Ta1 / Ta2) of the total equivalent amount (Ta1) of groups derived from the maleimide group (including the maleimide group) of component (c1) to the total equivalent amount (Ta2) of groups derived from the -NH2 group (including -NH2) of component (c2) is preferably 0.05 to 10, more preferably 1 to 5. When the equivalent ratio (Ta1 / Ta2) is within the above range, excellent high-frequency properties and better heat resistance, flame retardancy, and glass transition temperature tend to be obtained.

[0079] Maleimide compounds are preferably those containing a compound represented by the following general formula (C-2) from the viewpoint of high-frequency characteristics, insulation reliability, solubility in organic solvents, adhesion to conductors, and moldability.

[0080] [ka] (In the formula, X c1 and X c4 This is as explained in the general formulas (c1-1) and (c2-1) above.

[0081] (Method for producing modified maleimide compound (X)) Component (X) can be produced, for example, by reacting component (c1) and component (c2) in an organic solvent. Specifically, components (c1), (c2), and other components as needed are charged in predetermined amounts into a reactor, and a Michael addition reaction [hereinafter sometimes referred to as the "pre-reaction"] is carried out between components (c1) and (c2) to obtain a modified maleimide compound (X). While the reaction conditions are not particularly limited, from the viewpoint of suppressing gelation while obtaining good reactivity and workability, a reaction temperature of 50 to 160°C and a reaction time of 1 to 10 hours are preferred.

[0082] In the pre-reaction, 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. There are no particular restrictions on the amount of reaction catalyst used, but for example, it is 0.01 to 5 parts by mass per 100 parts by mass of the total amount of components (c1) and (c2).

[0083] Furthermore, in the pre-reaction, the solid content concentration of the reaction raw materials and the viscosity of the reaction solution may be adjusted by adding or concentrating an organic solvent as needed. The solid content concentration of the reaction raw materials is not particularly limited, but is preferably 10 to 90% by mass, and more preferably 20 to 80% by mass. If the solid content concentration of the reaction raw materials is above the lower limit, a sufficient reaction rate can be obtained, which tends to be advantageous in terms of manufacturing costs, and if it is below the upper limit, better solubility can be obtained, stirring efficiency improves, and gelation tends to be less likely.

[0084] The weight-average molecular weight (Mw) of the modified maleimide compound (X) is not particularly limited, but is preferably 400 to 10,000, more preferably 1,000 to 5,000, even more preferably 1,500 to 4,000, and particularly preferably 2,000 to 3,000.

[0085] (Content of component (C)) When the resin composition of this embodiment contains a thermosetting resin (C), the amount is not particularly limited, but from the viewpoint of high-frequency characteristics, heat resistance and moldability, it is preferably 5 to 80 parts by mass, more preferably 5 to 60 parts by mass, even more preferably 10 to 50 parts by mass, and particularly preferably 15 to 40 parts by mass, per 100 parts by mass of the total amount of resin components.

[0086] When the resin composition of this embodiment contains a thermosetting resin (C), the content ratio of polyphenylene ether derivative (A) to thermosetting resin (C) [(A) / (C)] is not particularly limited, but is preferably 5 / 95 to 80 / 20 by mass ratio, more preferably 6 / 94 to 60 / 40, even more preferably 8 / 92 to 40 / 60, and particularly preferably 10 / 90 to 20 / 80. When the above content ratio [(A) / (C)] is 5 / 95 or higher, better high-frequency characteristics and low hygroscopicity tend to be obtained. When the above content ratio [(A) / (C)] is 80 / 20 or lower, better heat resistance, moldability and processability tend to be obtained.

[0087] The resin composition of this embodiment preferably further contains one or more selected from the group consisting of a thermoplastic elastomer (D), a curing accelerator (E), and an inorganic filler (F). Each of these components will now be described.

[0088] <Thermoplastic elastomer (D)> The resin composition of this embodiment tends to have a good balance of high-frequency characteristics, moldability, adhesion to conductors, solder heat resistance, glass transition temperature, and thermal expansion coefficient due to the inclusion of thermoplastic elastomer (D). Thermoplastic elastomer (D) may be used alone or in combination of two or more types.

[0089] Examples of thermoplastic elastomers (D) include thermoplastic elastomers having structural units represented by the following general formula (D-1), wherein the structural units are derived from styrene (i.e., in the following general formula (D-1), R d1 is a hydrogen atom, n d1 It is preferable that the thermoplastic elastomer has structural units in which (the ratio of θ to θ is 0) (hereinafter sometimes referred to as styrene-based thermoplastic elastomer).

[0090] [ka] (In the formula, R d1 R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. d2 n represents an alkyl group having 1 to 5 carbon atoms. d1 (This represents an integer between 0 and 5.)

[0091] R d1 Examples of C1-C5 alkyl groups represented by include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, and n-pentyl group. R d1 Among the groups represented, the hydrogen atom is preferred. R d2 Examples of C1-C5 alkyl groups represented by include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, and n-pentyl groups. C1-C3 alkyl groups are preferred, and methyl groups are more preferred. n d1 This represents an integer between 0 and 5, preferably between 0 and 2, and more preferably 0. n d1 If is an integer greater than or equal to 2, then multiple R d1 They may be the same or they may be different.

[0092] Examples of structural units other than those derived from compounds that thermoplastic elastomer (D) possess include structural units derived from butadiene, isoprene, maleic acid, and maleic anhydride. The butadiene-derived structural units and isoprene-derived structural units are preferably hydrogenated. When hydrogenated, the butadiene-derived structural units become structural units that are a mixture of ethylene units and butylene units, and the isoprene-derived structural units become structural units that are a mixture of ethylene units and propylene units.

[0093] Examples of thermoplastic elastomers (D) include hydrogenated styrene-based thermoplastic elastomers such as hydrogenated styrene-butadiene-styrene block copolymer (SBS) and hydrogenated styrene-isoprene-styrene block copolymer (SIS). Among these, hydrogenated styrene-butadiene-styrene block copolymer (SBS) is preferred from the viewpoint of high-frequency characteristics, adhesion to conductors, heat resistance, glass transition temperature, and coefficient of thermal expansion.

[0094] Examples of hydrogenated styrene-butadiene-styrene block copolymers (SBS) include styrene-ethylene-butylene-styrene copolymer (SEBS), which is obtained by fully hydrogenating the carbon-carbon double bonds in the butadiene block, and styrene-butadiene-butylene-styrene (SBBS), which is obtained by partially hydrogenating the carbon-carbon double bonds at the 1,2-bonding sites in the butadiene block. In SEBS, full hydrogenation usually means 90% or more of the total carbon-carbon double bonds, but it may also be 95% or more, 99% or more, or even substantially 100%. In SBBS, the partial hydrogenation rate is, for example, 60-85% of the total carbon-carbon double bonds.

[0095] In SEBS, the content of styrene-derived structural units [hereinafter sometimes abbreviated as "styrene content"] is not particularly limited, but from the viewpoint of high-frequency characteristics, adhesion to conductors, heat resistance, glass transition temperature and coefficient of thermal expansion, 5 to 80% by mass is preferred, 10 to 70% by mass is more preferred, 15 to 60% by mass is even more preferred, and 20 to 50% by mass is particularly preferred. The melt flow rate (MFR) of SEBS is not particularly limited, but under measurement conditions of 230°C and a load of 2.16 kgf (21.2 N), it is preferably 0.1 to 20 g / 10 min, more preferably 1 to 15 g / 10 min, even more preferably 2 to 10 g / 10 min, and particularly preferably 3 to 7 g / 10 min.

[0096] In SBBS, the styrene content is not particularly limited, but from the viewpoint of high-frequency characteristics, adhesion to conductors, heat resistance, glass transition temperature, and coefficient of thermal expansion, 40 to 80% by mass is preferred, 50 to 75% by mass is more preferred, and 55 to 75% by mass is even more preferred. The MFR of SBBS is not particularly limited, but under measurement conditions of 190°C and a load of 2.16 kgf (21.2 N), it is preferably 0.1 to 10 g / 10 min, more preferably 0.5 to 8 g / 10 min, and even more preferably 1 to 6 g / 10 min.

[0097] The thermoplastic elastomer (D) may be acid-modified with maleic anhydride or the like. The acid value of the acid-modified thermoplastic elastomer (D) is not particularly limited, but is preferably 2 to 20 mg CH3ONa / g, more preferably 5 to 15 mg CH3ONa / g, and even more preferably 7 to 13 mg CH3ONa / g.

[0098] (Content of component (D)) When the resin composition of this embodiment contains thermoplastic elastomer (D), its content is not particularly limited, but is preferably 2 to 40 parts by mass, more preferably 5 to 30 parts by mass, even more preferably 8 to 25 parts by mass, and particularly preferably 10 to 20 parts by mass, based on 100 parts by mass of the total resin components. When the content of thermoplastic elastomer (D) is above the lower limit, better high-frequency properties and moisture resistance tend to be obtained. When the content of thermoplastic elastomer (D) is below the upper limit, good heat resistance, moldability, and processability tend to be obtained.

[0099] <Curing accelerator (E)> The resin composition of this embodiment, by containing a curing accelerator (E), tends to have improved curability, resulting in better high-frequency characteristics, heat resistance, adhesion to conductors, elastic modulus, and glass transition temperature. If the resin composition of this embodiment contains a curing accelerator (E), a suitable curing accelerator (E) can be appropriately selected according to the type of thermosetting resin (C) component used. The curing accelerator (E) may be used alone or in combination of two or more types.

[0100] (E) Examples of component include amine-based curing accelerators, imidazole-based curing accelerators, phosphorus-based curing accelerators, organometallic salts, acidic catalysts, and organic peroxides. In this embodiment, imidazole-based curing accelerators are not classified as amine-based curing accelerators. Examples of amine-based curing accelerators include amine compounds having primary to tertiary amines such as triethylamine, pyridine, tributylamine, and dicyandiamide; and quaternary ammonium compounds. Examples of imidazole-based curing accelerators include imidazole compounds such as methylimidazole, phenylimidazole, 2-undecylimidazole, and isocyanate-masquimidazole (for example, an addition reaction product of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole). Examples of phosphorus-based curing accelerators include tertiary phosphines such as triphenylphosphine, and quaternary phosphonium compounds such as the tri-n-butylphosphine addition product of p-benzoquinone. Examples of organometallic salts include carboxylates of manganese, cobalt, zinc, and others. Examples of acidic catalysts include p-toluenesulfonic acid. Examples of organic peroxides include 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'-di(t-butylperoxy)diisopropylbenzene. Among these, amine-based curing accelerators, imidazole-based curing accelerators, and phosphorus-based curing accelerators are preferred from the viewpoint of obtaining superior high-frequency characteristics, heat resistance, adhesion to conductors, elastic modulus, and glass transition temperature, and dicyandiamide, imidazole-based curing accelerators, and quaternary phosphonium compounds are more preferred, and it is even more preferable to use them in combination. Organic peroxides may also be used in combination, but from the viewpoint of the physical properties of the cured product, it is preferable not to contain organic peroxides.

[0101] (Content of component (E)) When the resin composition of this embodiment contains a curing accelerator (E), its content is not particularly limited, but is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, even more preferably 0.1 to 5 parts by mass, and particularly preferably 0.5 to 4 parts by mass, per 100 parts by mass of thermosetting resin (C). When the content of the curing accelerator (E) is within the above range, better high-frequency characteristics, heat resistance, storage stability, and moldability tend to be obtained.

[0102] <Inorganic filler (F)> The resin composition of this embodiment tends to exhibit superior low thermal expansion, high modulus of elasticity, heat resistance, and flame retardancy due to the inclusion of an inorganic filler (F). The inorganic filler (F) may be used alone or in combination of two or more types.

[0103] Examples of inorganic fillers (F) include silica, alumina, titanium oxide, mica, beryllium, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay (such as calcined clay), talc, aluminum borate, and silicon carbide. Among these, from the viewpoint of thermal expansion coefficient, elastic modulus, heat resistance, and flame retardancy, silica, alumina, mica, and talc are preferred as inorganic fillers (F), silica and alumina are more preferred, and silica is even more preferred. Examples of silica include precipitated silica, which is produced by a wet process and has a high water content, and dry-process silica, which is produced by a dry process and contains almost no bound water. Dry-process silica can be described by different manufacturing methods, such as crushed silica, fumed silica, and fused silica (fused spherical silica). Among these, fused spherical silica is preferred as the inorganic filler (F).

[0104] The average particle size of the inorganic filler (F) is not particularly limited, but is preferably 0.01 to 20 μm, more preferably 0.1 to 10 μm, even more preferably 0.2 to 1 μm, and particularly preferably 0.3 to 0.8 μm.

[0105] When the resin composition of this embodiment contains an inorganic filler (F), its content is not particularly limited, but from the viewpoint of thermal expansion coefficient, elastic modulus, heat resistance and flame retardancy, it is preferably 1 to 30% by mass, more preferably 1 to 25% by mass, even more preferably 1 to 20% by mass, even more preferably 2 to 15% by mass, and particularly preferably 2 to 8% by mass relative to the solid content.

[0106] When using an inorganic filler (F), a coupling agent may be used in combination as needed to improve the dispersibility of the inorganic filler (F) and the adhesion between the inorganic filler (F) and the organic components in the resin composition. Examples of coupling agents include silane coupling agents and titanate coupling agents. One type of coupling agent may be used alone, or two or more types may be used in combination. When using a coupling agent, the processing method may be a so-called integral blending method, in which the inorganic filler (F) is blended into the resin composition and then the coupling agent is added. However, it is preferable to use an inorganic filler that has been surface-treated with the coupling agent beforehand, either dry or wet. By adopting this method, the characteristics of the inorganic filler (F) can be expressed more effectively. Furthermore, the inorganic filler (F) may be used as a slurry pre-dispersed in an organic solvent, if necessary.

[0107] <Flame retardants, flame retardant enhancers, adhesion improvers> The resin composition of this embodiment may, as necessary, contain one or more components selected from the group consisting of flame retardants, flame retardant enhancers, and adhesion improvers, to the extent that the effects of this embodiment are not impaired. Each of these components may be used individually or in combination of two or more. Alternatively, the resin composition of this embodiment may not contain any of these components.

[0108] (Flame retardant) Examples of flame retardants include inorganic phosphorus-based flame retardants; organic phosphorus-based flame retardants; and metal hydrates such as aluminum hydroxide hydrate and magnesium hydroxide hydrate. While metal hydroxides can also be classified as inorganic fillers, they are classified as flame retardants if they can impart 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, phosphonic acid diesters and phosphinic acid esters; metal salts of phosphinic acid; organic nitrogen-containing phosphorus compounds; and cyclic organophosphorus compounds. Here, "metal salts" include, for example, lithium salts, sodium salts, potassium salts, calcium salts, magnesium salts, aluminum salts, titanium salts, and zinc salts.

[0109] (Flame retardant content) If the resin composition of this embodiment contains a flame retardant, the amount is not particularly limited, but is, for example, 0.1 parts by mass or more, 1 part by mass or more, 5 parts by mass or more, 10 parts by mass or more, 40 parts by mass or less, 30 parts by mass or less, 25 parts by mass or less, or 20 parts by mass or less, based on 100 parts by mass of the total resin components. Furthermore, the resin composition of this embodiment does not need to contain a flame retardant.

[0110] (Flame retardant) Examples of flame retardant additives include inorganic flame retardants such as antimony trioxide and zinc molybdate. If the resin composition of this embodiment contains a flame retardant additive, the amount is not particularly limited, but is preferably 0.1 to 20 parts by mass, and more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the total resin components. When the amount of flame retardant additive is within the above range, better chemical resistance tends to be obtained. Furthermore, the resin composition of this embodiment does not need to contain a flame retardant additive.

[0111] (Adhesion enhancer) Examples of adhesion-enhancing agents include nitrogen-containing compounds such as triazine derivatives and carbodiimides. If the resin composition of this embodiment contains an adhesion improver, the amount is not particularly limited, but is preferably 0.1 to 20 parts by mass, and more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the total resin components. When the adhesion improver content is within the above range, better copper foil peel strength tends to be obtained. Furthermore, the resin composition of this embodiment does not need to contain an adhesion improver.

[0112] <organic solvents> The resin composition of this embodiment may be a varnish-like resin composition containing an organic solvent, from the viewpoint of facilitating handling and facilitating the production of the prepreg described later. Examples of organic solvents include alcoholic 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; and ester solvents such as γ-butyrolactone. These organic solvents may be used individually or in combination of two or more types.

[0113] When the resin composition of this embodiment contains an organic solvent, the amount is not particularly limited, but it is preferable that the solid content concentration of the resin composition of this embodiment be 30 to 90% by mass, more preferably 40 to 80% by mass, and even more preferably 40 to 60% by mass. When the organic solvent content is within the above range, the resin composition becomes easier to handle, and the impregnation into the substrate and the appearance of the manufactured prepreg become good. Furthermore, it becomes easier to adjust the solid content concentration of the resin in the prepreg, as described later, and it tends to become easier to manufacture a prepreg with the desired thickness.

[0114] <Other ingredients> Furthermore, the resin composition of this embodiment may, as necessary, contain one or more other components selected from the group consisting of resin materials other than those listed above, coupling agents, antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, pigments, colorants, and lubricants, to the extent that it does not impair the effects of this embodiment. These components may be used individually or in combination of two or more. In addition, the resin composition of this embodiment may not contain these components. If the resin composition of this embodiment contains the above-mentioned other components, the content of each component is not particularly limited, but may be, for example, 0.01 parts by mass or more, or 10 parts by mass or less, 5 parts by mass or less, or 1 part by mass or less, based on 100 parts by mass of the total amount of resin components. Furthermore, the total content of components (A), (B), (C), (D), and (E) in the resin composition of this embodiment is not particularly limited, but is preferably 80 parts by mass or more, more preferably 90 parts by mass or more, and even more preferably 95 parts by mass or more, based on 100 parts by mass of the total resin components (however, all include 100 parts by mass).

[0115] <Dielectric properties (high frequency properties)> The dielectric constant (Dk) at 10 GHz when the resin composition of this embodiment is prepared as a test piece by the method described in the examples below is not particularly limited, but is preferably 3.0 or less, more preferably 2.7 or less, and even more preferably 2.5 or less. The smaller the dielectric constant (Dk), the better, and there is no particular limit to its lower limit, but considering the balance with other physical properties, it may be, for example, 2.0 or more, or 2.3 or more. The dielectric loss tangent (Df) at 10 GHz when the resin composition of this embodiment is prepared as a test piece by the method described in the examples below is not particularly limited, but is preferably 0.0045 or less, more preferably 0.0040 or less, and even more preferably 0.0035 or less. The smaller the dielectric loss tangent (Df), the better. There is no particular limit to its lower limit, but considering the balance with other physical properties, it may be, for example, 0.0020 or more, or 0.0025 or more. The dielectric constant (Dk) and dielectric loss tangent (Df) are values ​​obtained in accordance with the cavity resonator perturbation method, and more specifically, are values ​​measured by the method described in the examples. In this specification, when the term dielectric constant is used, it refers to the relative dielectric constant.

[0116] The resin composition of this embodiment can be produced by mixing component (A), component (B), and any optional components used in combination as needed, in a known manner. In this case, each component may be dissolved or dispersed in the organic solvent while stirring. The mixing order, temperature, time, and other conditions are not particularly limited and can be set arbitrarily.

[0117] [Metal foil with resin coating] The resin-coated metal foil of this embodiment has a layer of the resin composition of this embodiment on the metal foil. Specifically, the resin-coated metal foil can be manufactured by applying the resin composition of this embodiment onto a metal foil and partially curing (B-stage) the resin composition in a drying oven. The drying conditions are not particularly limited, but the drying temperature is preferably 80 to 180°C, more preferably 110 to 160°C. There are no particular restrictions on the coating method, and known coating machines such as die coaters, comma coaters, bar coaters, kiss coaters, and roll coaters can be used. Examples of metal foils used in resin-coated metal foils include copper foil and aluminum foil, but other metal foils can also be used. Among these, copper foil is preferred.

[0118] [Prepreg] The prepreg of this embodiment is a prepreg comprising the resin composition of this embodiment and a sheet-like fiber-reinforced substrate. Here, the expression "comprising the resin composition and a sheet-like fiber-reinforced substrate" includes cases in which the resin composition and the sheet-like fiber-reinforced substrate are contained as they are, and cases in which the resin composition and the sheet-like fiber-reinforced substrate are contained in which at least a portion of the components of the resin composition have reacted. The prepreg can be formed using the resin composition of this embodiment and a sheet-like fiber-reinforced substrate. For example, the resin composition of this embodiment can be impregnated or coated onto a sheet-like fiber-reinforced substrate, and then heated and dried in a drying oven at a temperature of 80 to 200°C for 1 to 30 minutes to partially cure (B-stage) the resin composition. Hereinafter, B-stage refers to reaching the B-stage state as defined in JIS K6900 (1994). The solid content derived from the resin composition in the prepreg of this embodiment is not particularly limited, but is preferably 30 to 90% by mass, more preferably 35 to 80% by mass, even more preferably 40 to 70% by mass, and particularly preferably 45 to 60% by mass. When the solid content derived from the resin composition in the prepreg is within the above range, better moldability tends to be obtained when it is made into a laminate.

[0119] As the sheet-like fiber reinforcement base material for the prepreg, known materials used in laminates for various electrical insulating materials can be used. Examples of materials for the sheet-like fiber reinforcement base material include inorganic fibers such as E-glass, D-glass, S-glass, and Q-glass; organic fibers such as polyimide, polyester, and tetrafluoroethylene; and mixtures thereof. These sheet-like fiber reinforcement base materials can be in the form of woven fabric, nonwoven fabric, rawhide, chopped strand mat, or surfacing mat. Furthermore, the thickness of the sheet-like fiber reinforcement base material is not particularly limited, and for example, materials with a thickness of 0.02 to 0.5 mm can be used. In addition, from the viewpoint of impregnation of the resin composition, heat resistance, moisture resistance, and processability when used as a laminate, materials that have been surface-treated with coupling agents or those that have been mechanically opened can be used.

[0120] The following hot-melt method or solvent method can be used as a method for impregnating or coating a sheet-like fiber-reinforced substrate with a resin composition. The hot melt method involves (1) coating a coated paper with good release properties from the resin composition with the resin composition and then laminating it onto a sheet-like fiber-reinforced substrate, or (2) directly coating the sheet-like fiber-reinforced substrate with a die coater, without including an organic solvent in the resin composition. On the other hand, the solvent method involves incorporating an organic solvent into a resin composition, immersing a sheet-like fiber-reinforced substrate in the resulting resin composition to impregnate the sheet-like fiber-reinforced substrate with the resin composition, and then drying it.

[0121] [Laminated board] The laminate of this embodiment is a laminate containing (i) the resin-coated metal foil of this embodiment or (ii) the prepreg and metal foil of this embodiment. The laminate of this embodiment can be obtained by heating and pressing one resin-coated metal foil of this embodiment, or by arranging two resin-coated metal foils so that the metal foil forms the outer layer, and then heating and pressing them. Alternatively, the laminate can be obtained by arranging metal foil on one or both sides of one prepreg of this embodiment, or by arranging metal foil on one or both sides of two or more prepregs of this embodiment stacked together, and then heating and pressing them. Laminates having metal foil are sometimes referred to as metal-clad laminates. The metal used for the metal foil is not particularly limited as long as it is used for electrical insulating material applications. However, from the viewpoint of conductivity, it may be copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, or an alloy containing one or more of these metal elements. Copper and aluminum are preferred, and copper is more preferred. In this embodiment, the laminate and metal-clad laminate have the resin sheet in a C-staged state. In other words, the laminate of this embodiment has a C-staged prepreg, and the metal-clad laminate of this embodiment has a C-staged resin-coated metal foil, or a C-staged prepreg and metal foil. Hereinafter, C-staged state in this specification means being in a C-staged state as defined in JIS K6900 (1994).

[0122] [Multilayer printed circuit board] The multilayer printed circuit board of this embodiment comprises (i) a resin-coated metal foil of this embodiment, (ii) a prepreg of this embodiment, or (iii) a laminate of this embodiment. The multilayer printed circuit board of this embodiment does not necessarily have to contain (i) to (iii) in their original form; for example, it may also contain (iii) after it has been subjected to processing such as drilling, metal plating, or etching of the metal foil to form circuits. The multilayer printed circuit board of this embodiment can be manufactured by using the resin-coated metal foil, prepreg, or laminate of this embodiment and performing circuit formation processing such as drilling, metal plating, etching of the metal foil, and multilayering processing by known methods.

[0123] [Semiconductor Packages] The semiconductor package of this embodiment includes the multilayer printed circuit board of this embodiment and semiconductor elements. In other words, the semiconductor package of this embodiment is formed by mounting semiconductor elements on the multilayer printed circuit board of this embodiment. The semiconductor package of this embodiment can be manufactured, for example, by mounting semiconductor elements such as semiconductor chips and memory at predetermined positions on the multilayer printed circuit board of this embodiment using known methods, and then sealing the semiconductor elements with a sealing resin or the like.

[0124] While preferred embodiments of this disclosure have been described above, these are merely examples for illustrative purposes and are not intended to limit the scope of this disclosure to these embodiments only. This disclosure may also be implemented in various forms different from those described above, without departing from its essence. [Examples]

[0125] The embodiment will be described in detail below with reference to examples. However, this embodiment is not limited to the following examples.

[0126] In each example, the weight-average molecular weight (Mw) was measured by the following method. The results were 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. Device: Pump: L-6200 model [manufactured by Hitachi High-Technologies Corporation] Detector: L-3300 type RI [manufactured by Hitachi High-Technologies Corporation] Column Oven: L-655A-52 [Manufactured by Hitachi High-Technologies Corporation] Columns: Guard column; "TSK Guardcolumn HHR-L" + Columns; "TSKgel G4000HHR" + "TSKgel G2000HHR" (all manufactured by Tosoh Corporation, product names) Column sizes: 6.0 x 40 mm (guard column), 7.8 x 300 mm (column) Eluent: Tetrahydrofuran Sample concentration: 30 mg / 5 mL Injection volume: 20μL Flow rate: 1.00mL / min Measurement temperature: 40℃

[0127] [Manufacturing Example 1: Manufacturing of Modified Maleimide Compound (X1)] Into a 5-liter reaction vessel that can be heated and cooled, equipped with a thermometer, a stirring device, and a moisture quantifier with a reflux condenser, 100 parts by mass of 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, 13.5 parts by mass of 3,3'-diethyl-4,4'-diaminodiphenylmethane, and 171 parts by mass of propylene glycol monomethyl ether were charged and reacted for 2 hours while refluxing. This was concentrated at the reflux temperature over 3 hours to produce a modified maleimide compound (X1)-containing liquid with a solid content concentration of 65% by mass. The weight average molecular weight (Mw) of the obtained modified maleimide resin (X1) was about 2,700.

[0128] [Examples 1 to 5, Comparative Examples 1 to 2] (Preparation of resin composition) Each component described in Table 1 was stirred and mixed at room temperature together with 58 parts by mass of toluene and 10 parts by mass of methyl isobutyl ketone according to the blending composition described in Table 1 to prepare a resin composition with a solid content concentration of 45 to 55% by mass. In each example and comparative example, in order to unify the filler content, the total content of the fluororesin filler (B) and the inorganic filler (F) was adjusted to be equal. (Production of copper foil with resin) The resin composition obtained in each example was coated on a copper foil (MT18FL1.5, manufactured by Mitsui Mining & Smelting Co., Ltd.) with a thickness of 0.0195 mm using a coater, and then heat-dried at 120°C for 3 minutes to produce a copper foil with resin having a coating thickness of 25 μm. (Production of laminate and production of resin plate) Furthermore, the resin composition was applied to a 0.050 mm thick PET film using a coating machine, and then heated and dried at 120°C for 3 minutes to produce a resin-coated PET film with a coating thickness of 25 μm. The resin sides of these resin-coated PET films were bonded together using vacuum pressure lamination (temperature 110°C, pressure 0.5 MPa). In addition, one side of the PET film was peeled off, and the peeled sides were bonded together, and the layers were laminated until the resin thickness reached 325 μm. The PET on both sides of this 325 μm thick resin-coated PET film was peeled off, and 18 μm thick low-profile copper foil (BF-ANP18, M-side Rz: 1.5 μm, manufactured by CIRCUIT FOIL Co., Ltd.) was laminated above and below the resin so that the M-side was in contact with the resin, and this laminate was placed in a 300 μm thick mold. Next, a double-sided copper-clad laminate was produced by heating and pressurizing under the conditions of temperature 230°C, pressure 3.0 MPa, and time 90 minutes. The outer copper foil layer of this double-sided copper-clad laminate was removed by immersion in a copper etching solution (10% by mass solution of ammonium persulfate, manufactured by Mitsubishi Gas Chemical Company, Inc.) to produce a resin plate with a thickness of 300 μm.

[0129] [Evaluation Method] Each measurement and evaluation was performed according to the method described below. The results are shown in Table 1.

[0130] (1. Measurement of dielectric properties (high-frequency properties)) For each example, resin plates were fabricated and cut to a length of 60 mm and a width of 2 mm to serve as test specimens. The dielectric constant and dielectric loss tangent were measured using the cavity resonator perturbation method. The measuring instrument used was the Agilent Technologies N5227A vector network analyzer, the cavity resonator was the CP129 (10 GHz band resonator) manufactured by Kanto Electronics Applied Development Co., Ltd., and the measurement program was CPMA-V2. Measurements were performed under conditions of a frequency of 10 GHz and a measurement temperature of 25°C.

[0131] (2. Evaluation of edge powder shedding when cutting resin-coated copper foil) When the resin-coated copper foil prepared in each example was cut using the "Refined Slitter W-650" cutting machine (slit blade size: 98mm x 66mm, thickness: 2mm, see Figure 1, manufactured by Soltec Industries Co., Ltd.), the amount of resin powder adhering to the slit blade was visually observed. When there was almost no resin powder adhering to the slit blade (see Figure 2), it was judged as "A," and when there was a large amount of resin powder adhering to the slit blade (see Figure 3), it was judged as "C."

[0132] [Table 1]

[0133] The abbreviations and other symbols for each material in Table 1 are as follows: [(A) Component: Polyphenylene ether derivative] A-1: A polyphenylene ether having methacrylic groups at both ends of the molecule (weight-average molecular weight (Mw); 1,700). This corresponds to the compound represented by the general formula (A-4) above. [(B) Component: Fluororesin filler] B-1: PTFE filler; particulate, average particle size: 3 μm [(C) Component: Thermosetting resin] • C-1: Modified maleimide compound (X1) prepared in Manufacturing Example 1 [(D) Component: Thermoplastic elastomer] • D-1: Maleic anhydride-modified hydrogenated styrene thermoplastic elastomer (maleic anhydride-modified SEBS), acid value 10 mg CH3ONa / g, styrene content 30%, MFR 5.0 g / 10 min (MFR measurement conditions: Measured at 230°C and under a load of 2.16 kg, in accordance with ISO 1133.) [(E) Ingredient: Curing accelerator] • E-1: Addition reaction product of p-benzoquinone with tri-n-butylphosphine • E-2:2-undecylimidazole ·E-3: Dicyandiamide [(F) Component: Inorganic filler] F-1: Spherical fused silica: Average particle size 0.5 μm, 70% by mass of methyl isobutyl ketone slurry [Flame retardant] • 4,4'-biphenol-bis(di-2,6-xylenyl phosphate), melting point: 184°C, average particle size: 1.5 μm, see structural formula below. [ka]

[0134] As is clear from the results shown in Table 1, the resin-coated copper foils and laminates of Examples 1 to 5, which were made using the resin composition of this embodiment, exhibit superior high-frequency characteristics compared to the resin-coated copper foils and laminates of Comparative Examples 1 and 2, and also show that powder shedding at the edges of the resin-coated metal foil was suppressed during cutting. In particular, a comparison between Example 5 and Comparative Example 1 shows that using components (A) and (B) in combination significantly improves the dielectric constant (Dk) and suppresses powder shedding at the edges of the resin-coated metal foil during cutting.

[0135] The resin composition of this embodiment exhibits excellent dielectric properties in the high frequency band of 10 GHz or higher, and also suppresses powder shedding at the edges when cutting the resin-coated metal foil. Therefore, resin-coated metal foil, prepregs, laminates, multilayer printed circuit boards, semiconductor packages, etc., obtained using this resin composition are suitable for electronic component applications that handle high-frequency signals.

Claims

1. A resin composition containing a polyphenylene ether derivative (A) and a fluororesin filler (B), A resin composition wherein component (A) has an ethylenically unsaturated bond-containing group at its molecular terminus, and the ethylenically unsaturated bond-containing group is a maleimide group or a group containing a heteroatom and an ethylenically unsaturated bond.

2. The resin composition according to claim 1, wherein the group comprising the heteroatom and the ethylenically unsaturated bond is a group represented by the following general formula (A-1). 【Chemistry 1】 (In the formula, R a1 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. * indicates the bond position.)

3. The resin composition according to claim 1 or 2, wherein the ethylenically unsaturated bond-containing group is a (meth)acrylic group.

4. The resin composition according to any one of claims 1 to 3, wherein the weight-average molecular weight (Mw) of component (A) is 500 to 7,000.

5. The resin composition according to any one of claims 1 to 4, wherein the component (B) is at least one selected from the group consisting of polytetrafluoroethylene (PTFE) filler, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA) filler, tetrafluoroethylene-hexafluoropropylene copolymer (FEP) filler, tetrafluoroethylene-ethylene copolymer (ETFE) filler, and polychlorotrifluoroethylene (PCTFE) filler.

6. The resin composition according to any one of claims 1 to 5, wherein the average particle size of component (B) is 0.1 to 10 μm.

7. The resin composition according to any one of claims 1 to 6, wherein the content of component (B) is 1% by mass or more and less than 50% by mass with respect to the solid content of the resin composition.

8. The resin composition according to any one of claims 1 to 7, wherein the content of component (B) is 1 to 40% by mass relative to the solid content of the resin composition.

9. The resin composition according to any one of claims 1 to 8, further comprising one or more thermosetting resins (C) selected from the group consisting of epoxy resins, cyanate resins, and maleimide compounds.

10. The resin composition according to claim 9, wherein the (C) component contains the maleimide compound, and the maleimide compound is a modified maleimide compound having a structural unit derived from a maleimide compound (c1) having at least two N-substituted maleimide groups and a structural unit derived from an amine compound (c2) having a primary amino group.

11. The resin composition according to claim 10, wherein the modified maleimide compound is a compound represented by the following general formula (C-1). 【Chemistry 2】 (In the formula, X ｃ１ and X ｃ２ These are each independently divalent organic groups.

12. The resin composition according to any one of claims 9 to 11, wherein the content ratio of component (A) to component (C) [(A) / (C)] is 5 / 95 to 80 / 20 by mass ratio.

13. Furthermore, the resin composition according to any one of claims 1 to 12 contains one or more selected from the group consisting of a thermoplastic elastomer (D), a curing accelerator (E), and an inorganic filler (F).

14. A resin-coated metal foil having a layer of the resin composition described in any one of claims 1 to 13 on the metal foil.

15. A prepreg comprising the resin composition according to any one of claims 1 to 13 and a sheet-like fiber-reinforced substrate.

16. (i) a resin-coated metal foil as described in claim 14, or (ii) a laminate containing a prepreg and metal foil as described in claim 15.

17. A multilayer printed circuit board comprising (i) a resin-coated metal foil as described in claim 14, (ii) a prepreg as described in claim 15, or (iii) a laminate as described in claim 16.

18. A semiconductor package comprising a multilayer printed circuit board according to claim 17 and a semiconductor element.

Images