Resin composition, prepreg, laminate, multilayer printed wiring board and semiconductor package

Abstract

The present invention relates to a resin composition comprising a phosphate flame retardant (A) and a polyphenylene ether derivative (B), wherein the phosphate flame retardant (A) has an aromatic hydrocarbon group containing two or more aromatic ring structures, and the polyphenylene ether derivative (B) has a group containing an ethylenically unsaturated bond at both ends.

Description

Technical Field

[0001] The present invention relates to a resin composition, a prepreg, a laminate, a multilayer printed wiring board and a semiconductor package. Background Art

[0002] In mobile communication devices represented by mobile phones, network infrastructure equipment such as base station devices, servers, routers, large computers, etc., the high speed and large capacity of the signals used are developing year by year. Along with this, the printed wiring boards carried by these electronic devices need to cope with high frequencies, requiring substrate materials with excellent dielectric properties (low dielectric constant and low dielectric loss tangent; hereinafter, sometimes referred to as high-frequency characteristics) in high-frequency bands (for example, above 10GHz) that can reduce transmission losses. In recent years, as an application for processing such high-frequency signals, in addition to the above-mentioned electronic devices, the implementation plan and practical application of new systems for processing high-frequency wireless signals in the ITS field (related to automobiles and transportation systems) and indoor short-range communication fields are also being promoted. Therefore, it is expected that low transmission loss substrate materials will also be required for printed wiring boards carried by these devices in the future.

[0003] In addition, in recent years, due to the increased awareness of environmental issues, environmental considerations have become indispensable for electronic devices and electronic components. For a long time, regarding the halogen-based flame retardants used in plastic products as a whole, it has been reported that decabromodiphenyl ether, the most representative bromine-based flame retardant, generates toxic brominated dibenzodioxins and furans when burned, and its safety has been questioned. Therefore, from the perspective of environmental considerations, the introduction of halogen-free products that do not use the previous halogen-containing bromine-based flame retardants is being promoted. It should be noted that halogen-free refers to the situation where halogen atoms are completely free or their content is extremely small. For example, the Japan Electronic Circuit Industry Association defines the definition of halogen-free printed wiring board copper-clad laminate as the content of chlorine (Cl) and bromine (Br) is 900ppm or less, respectively, and the total content of chlorine and bromine is 1500ppm or less.

[0004] In order to impart flame retardancy to halogen-free printed wiring board materials, phosphorus-containing flame retardants are generally used, but flame retardancy of halogen-free materials requires a large amount of flame retardants, so the dielectric properties of the flame retardants have a gradually increasing impact on the dielectric properties of the printed wiring board itself. However, flame retardants are also materials with poor dielectric properties among the materials constituting the printed wiring board materials, so sometimes the dielectric properties of the printed wiring board become insufficient due to an increase in the amount of addition, which becomes an obstacle to improving the dielectric properties of the printed wiring board.

[0005] Patent document 1 discloses a resin composition having excellent dielectric properties and having excellent heat resistance and flame retardancy of a cured product, the resin composition comprising a modified polyphenylene ether compound, a cross-linking curing agent and a flame retardant, wherein the flame retardant comprises a compatible phosphorus compound compatible with a mixture of the modified polyphenylene ether compound and the cross-linking curing agent, and an incompatible phosphorus compound incompatible with the mixture.

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: Japanese Patent Application Publication No. 2015-86330 Summary of the invention

[0009] Problems to be solved by the invention

[0010] However, in recent years, it is urgently desired to develop a resin composition with further improved dielectric properties above the 10 GHz band that can be used in the fifth generation mobile communication system (5G) antenna using radio waves in a frequency band exceeding 6 GHz and the millimeter wave radar using radio waves in a frequency band of 30 to 300 GHz. That is, for the resin composition, it is expected to have sufficient flame retardancy and better dielectric properties than before. Although the technology of patent document 1 has observed a certain improvement in flame retardancy, it cannot fully cope with the high requirements for dielectric properties in recent years.

[0011] In view of the above situation, an object of the present invention is to provide a resin composition having sufficient flame retardancy and exhibiting excellent dielectric properties in a high frequency band of 10 GHz or higher, and a prepreg, a laminate, a multilayer printed wiring board and a semiconductor package using the resin composition.

[0012] Another object of the present invention is to provide a combination of components contained in a resin composition that has sufficient flame retardancy and can exhibit excellent dielectric properties in a high frequency band of 10 GHz or higher.

[0013] Means for solving problems

[0014] The present inventors have conducted intensive studies to solve the above problems and have found that a resin composition containing a flame retardant having a specific molecular structure and a polyphenylene ether derivative has sufficient flame retardancy and exhibits excellent dielectric properties, thereby completing the present invention.

[0015] That is, the present invention relates to the following [1] to

[15] .

[0016] [1] A resin composition comprising:

[0017] A phosphate ester flame retardant (A) having an aromatic hydrocarbon group having two or more aromatic ring structures; and

[0018] A polyphenylene ether derivative (B) having an ethylenically unsaturated bond-containing group at both terminals.

[0019] [2] The resin composition according to the above [1], wherein the aromatic hydrocarbon group containing two or more aromatic ring structures is a divalent aromatic hydrocarbon group in which two or more aromatic rings are bonded to each other via a single bond or a connecting group having 5 or less carbon atoms, or a divalent condensed polycyclic aromatic hydrocarbon group containing two or more aromatic ring structures.

[0020] [3] The resin composition according to [1] or [2], wherein the component (A) is a compound represented by the following general formula (A-1).

[0021] [Chemical formula 1]

[0022]

[0023] (Where R a1 ~R a4 Each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. a1 It represents a divalent group represented by the following general formula (A-2) or a divalent condensed polycyclic aromatic hydrocarbon group containing two or more aromatic ring structures. a1 ~n a4 Each independently represents an integer from 0 to 5, and n a5 Indicates an integer from 1 to 5. )

[0024] [Chemical formula 2]

[0025]

[0026] (Where R a5 and R a6 Each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. a2 represents an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a thioether group, a sulfonyl group, a carbonyloxy group, a keto group, or a single bond. a6 and n a7 Each independently represents an integer from 0 to 4. a8 Indicates an integer from 1 to 3. )

[0027] [4] The resin composition according to any one of [1] to [3] above, wherein the content of phosphorus atoms derived from the component (A) is 0.2 to 5% by mass in the solid content of the resin composition excluding the inorganic filler.

[0028] [5] The resin composition according to any one of [1] to [4], wherein the ethylenically unsaturated bond-containing group of the component (B) is a (meth)acryloyl group.

[0029] [6] The resin composition according to any one of [1] to [5] above, wherein the weight average molecular weight (Mw) of the component (B) is 500 to 7,000.

[0030] [7] The resin composition according to any one of [1] to [6] above, further comprising one or more thermosetting resins (C) selected from epoxy resins, cyanate resins and maleimide compounds.

[0031] [8] The resin composition according to the above [7], wherein the component (C) contains the maleimide compound, which has a structural unit derived from a maleimide compound (c1) having at least two N-substituted maleimide groups and a structural unit derived from a diamine compound (c2).

[0032] [9] The resin composition according to [8] above, wherein the maleimide compound is a modified maleimide compound represented by the following general formula (C-2).

[0033] [Chemical formula 3]

[0034]

[0035] (Where X c1 and X c4 Each is independently a divalent organic group.)

[0036]

[10] The resin composition according to any one of [1] to [9] above, further comprising one or more selected from a styrene-based thermoplastic elastomer (D), a curing accelerator (E) and an inorganic filler (F).

[0037]

[11] A prepreg comprising the resin composition according to any one of [1] to

[10] above and a sheet-like fiber-reinforced base material.

[0038]

[12] A laminate comprising the prepreg according to

[11] above and a metal foil.

[0039]

[13] A multilayer printed wiring board comprising the prepreg described in

[11] or the laminate described in

[12] .

[0040]

[14] A semiconductor package comprising a semiconductor element mounted on the multilayer printed wiring board described in

[13] .

[0041]

[15] A method for producing a laminated plate, comprising the step of heat-curing the resin composition described in any one of [1] to

[10] above, wherein:

[0042] The melting point of the above-mentioned component (A) is 50 to 250°C.

[0043] The heating and curing temperature is above the melting point of the component (A).

[0044] The component (A) in the resin composition before heat curing has a particle shape.

[0045] Effects of the Invention

[0046] According to the present invention, a resin composition having sufficient flame retardancy and exhibiting excellent dielectric properties in a high frequency band of 10 GHz or higher, and a prepreg, a laminate, a multilayer printed wiring board, and a semiconductor package using the resin composition can be provided. DETAILED DESCRIPTION

[0047] In the numerical ranges described in this specification, the upper limit or lower limit of the numerical range can be replaced by the values ​​shown in the embodiments. In addition, the lower limit and upper limit of the numerical range can be arbitrarily combined with the lower limit or upper limit of other numerical ranges.

[0048] In addition, each component and material exemplified in this specification can be used alone or in combination of two or more unless otherwise specified. In this specification, when there are multiple substances equivalent to each component in the composition, the content of each component in the composition refers to the total amount of the multiple substances present in the composition unless otherwise specified.

[0049] Any combination of the matters described in this specification is also included in the present invention.

[0050] [Resin composition]

[0051] The resin composition of this embodiment contains:

[0052] A phosphate ester flame retardant (A) having an aromatic hydrocarbon group having two or more aromatic ring structures [hereinafter, sometimes referred to as "phosphate ester flame retardant (A)" or "component (A)"]; and

[0053] The polyphenylene ether derivative (B) has an ethylenically unsaturated bond-containing group at both ends [hereinafter, sometimes simply referred to as "polyphenylene ether derivative (B)" or "component (B)"]. ].

[0054] Hereinafter, each component contained in the resin combination of the present embodiment is described.It should be noted that, in each component described below, there is also a component that can contain halogen, but from the viewpoint of halogen-free, chlorine content and bromine content are each preferably below 900 mass ppm, more preferably below 500 mass ppm, further preferably below 100 mass ppm, and particularly preferably do not contain substantially.In addition, from the same viewpoint, the total amount of chlorine content and bromine content is preferably below 1500 mass ppm, more preferably below 500 mass ppm, further preferably below 100 mass ppm, and particularly preferably do not contain substantially.The content of halogen atoms can be measured by ion chromatography.

[0055] In addition, as the "halogen atom" in the following description, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. can be illustrated.

[0056] <Phosphate ester flame retardant (A)>

[0057] The phosphate ester flame retardant (A) has an aromatic hydrocarbon group having two or more aromatic ring structures [hereinafter, sometimes simply referred to as “aromatic hydrocarbon group (a)”]. ].

[0058] The resin composition of the present embodiment has sufficient flame retardancy and exhibits excellent dielectric properties by containing the phosphate ester flame retardant (A). The reason for this is not yet clear, but is presumed as follows.

[0059] This is considered to be because the phosphate ester flame retardant (A) has an aromatic hydrocarbon group containing two or more aromatic ring structures in the molecule, and has a highly crystalline structure in which molecules are closely packed together due to the interaction of the two or more aromatic ring structures, thereby reducing molecular vibration, which is one of the causes of deterioration of dielectric properties.

[0060] The phosphate ester flame retardant (A) may be used alone or in combination of two or more.

[0061] The aromatic hydrocarbon group (a) may be a monovalent group or a divalent or higher group, and is preferably a divalent group. When the aromatic hydrocarbon group (a) is a divalent group, the divalent aromatic hydrocarbon group (a) is preferably a divalent group in which two phosphate bonds are connected (i.e., a group forming =P(=O)-O-aromatic hydrocarbon group (a)-OP(=O)=).

[0062] The divalent aromatic hydrocarbon group (a) is preferably a divalent aromatic hydrocarbon group in which two or more aromatic rings are bonded to each other via a single bond or a connecting group having 5 or less carbon atoms [hereinafter, sometimes referred to as “aromatic hydrocarbon group (a1)”.], or a divalent condensed polycyclic aromatic hydrocarbon group containing two or more aromatic ring structures [hereinafter, sometimes referred to as “aromatic hydrocarbon group (a2)”.], and more preferably an aromatic hydrocarbon group (a1).

[0063] (Aromatic hydrocarbon group (a1))

[0064] Examples of the two or more aromatic rings contained in the aromatic hydrocarbon group (a1) include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, etc. Among them, a benzene ring is preferred from the viewpoint of high frequency characteristics, adhesion to a conductor, and flame retardancy.

[0065] The aromatic hydrocarbon group formed by these aromatic rings may or may not be substituted by a substituent. Examples of the substituent include aliphatic hydrocarbon groups having 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and n-pentyl; and halogen atoms such as fluorine, chlorine, bromine, and iodine.

[0066] The aromatic hydrocarbon group (a1) preferably contains a substituted or unsubstituted phenylene group, and more preferably contains an unsubstituted phenylene group, from the viewpoint of high-frequency characteristics, adhesion to a conductor, and flame retardancy.

[0067] The two or more aromatic rings contained in the aromatic hydrocarbon group (a1) may be the same as or different from each other.

[0068] Examples of the linking group having 5 or less carbon atoms contained in the aromatic hydrocarbon group (a1) include a divalent hydrocarbon group having 1 to 5 carbon atoms, a divalent heteroatom-containing group having 5 or less carbon atoms, and a divalent group having 1 to 5 carbon atoms formed by linking a hydrocarbon group and a heteroatom-containing group. It should be noted that the "carbon number of 5 or less" herein also includes the case where the carbon number is 0.

[0069] Examples of the divalent hydrocarbon group having 1 to 5 carbon atoms include alkylidene groups having 1 to 5 carbon atoms such as methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, and 1,5-pentylene; and alkylidene groups having 2 to 5 carbon atoms such as ethylidene, propylidene, isopropylidene, butylidene, isobutylidene, pentylidene, and isopentylidene. Examples of the divalent heteroatom-containing group having 5 or less carbon atoms include ether groups, thioether groups, sulfonyl groups, carbonyloxy groups, and keto groups.

[0070] From the viewpoint of high-frequency characteristics, adhesion to a conductor, and flame retardancy, the aromatic hydrocarbon group (a1) is preferably a divalent group represented by the following general formula (A-2).

[0071] [Chemical formula 4]

[0072]

[0073] (Where R a5 and R a6 Each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. a2 represents an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a thioether group, a sulfonyl group, a carbonyloxy group, a keto group, or a single bond. a6 and n a7 Each independently represents an integer from 0 to 4. a8 Indicates an integer from 1 to 3. )

[0074] As X in the above general formula (A-2) a2 Examples of the alkylene group having 1 to 5 carbon atoms include methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, and 1,5-pentylene.

[0075] As X a2 Examples of the alkylidene group having 2 to 5 carbon atoms include ethylidene, propylidene, isopropylidene, butylidene, isobutylidene, pentylidene and isopentylidene.

[0076] X a2 Among the groups shown, from the viewpoints of high-frequency characteristics, adhesion to a conductor, and flame retardancy, a methylene group, an isopropylidene group, and a single bond are preferred, and a single bond is more preferred.

[0077] As R in the above general formula (A-2) a5 and R a6 Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl and n-pentyl.

[0078] From the viewpoint of high frequency characteristics, adhesion to conductors and flame retardancy, n in the general formula (A-2) is a6 and n a7 It is preferably an integer of 0 to 3, more preferably 0 or 1, and further preferably 0. a6 or a7 When the integer is 2 or more, multiple R a5 Each other or multiple R a6 They may be the same as or different from each other.

[0079] In the above general formula (A-2), n a8 Preferably it is 1 or 2, more preferably 1. a8 When the number of X is an integer greater than 2,a2 Each other and multiple n a7 They may be the same as or different from each other.

[0080] From the viewpoints of high-frequency characteristics, adhesion to conductors and flame retardancy, the divalent group represented by the general formula (A-2) is preferably a divalent group represented by the following formula (A-2-1) or a divalent group represented by the following formula (A-2-2), and more preferably a divalent group represented by the following formula (A-2-2).

[0081] [Chemical formula 5]

[0082]

[0083] (Aromatic hydrocarbon group (a2))

[0084] The above-mentioned aromatic hydrocarbon group (a2) is a divalent condensed polycyclic aromatic hydrocarbon group containing two or more aromatic ring structures. In the present embodiment, "condensed polycyclic aromatic hydrocarbon" refers to an aromatic hydrocarbon having a condensed ring with two or more ring structures and two or more rings having two or more atoms, for example, naphthalene, anthracene, pyrene, etc. can be cited. Therefore, as an aromatic hydrocarbon group (a2), a divalent group formed by removing two hydrogen atoms from these condensed polycyclic aromatic hydrocarbons can be cited. These condensed polycyclic aromatic hydrocarbon groups may be substituted with a substituent or may not be substituted with a substituent. As a substituent, the same substituent as the substituent that the aromatic ring contained in the above-mentioned aromatic hydrocarbon group (a1) may have can be cited.

[0085] The number of phosphorus atoms in one molecule of the phosphate flame retardant (A) is not particularly limited, but is preferably 1 to 10, more preferably 2 to 5, further preferably 2 or 3, and particularly preferably 2, from the viewpoint of high-frequency characteristics, adhesion to conductors, and flame retardancy. When the phosphate flame retardant (A) has two or more phosphorus atoms, it is preferably a condensed phosphoric acid ester in which a phosphoric acid ester bond formed by one phosphorus atom and a phosphoric acid ester bond formed by other phosphorus atoms are connected via the above-mentioned divalent aromatic hydrocarbon group (a).

[0086] The phosphate flame retardant (A) may be a monovalent phosphate, a divalent phosphate, or a trivalent phosphate. From the viewpoint of high frequency characteristics, adhesion to a conductor, and flame retardancy, a trivalent phosphate is preferred.

[0087] The phosphate group of the phosphate flame retardant (A) may be any of alkyl esters, aryl esters, arylalkyl esters, etc., and is preferably an aryl ester from the viewpoint of high frequency characteristics, adhesion to a conductor, and flame retardancy. That is, the phosphate flame retardant (A) is preferably an aromatic phosphate compound.

[0088] Examples of the aryl group constituting the aryl ester include substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, etc. Examples of the substituent of the aryl group include hydrocarbon groups having 1 to 5 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and n-pentyl; and halogen atoms. Among them, the aryl group is preferably unsubstituted phenyl or 2,5-dimethylphenyl.

[0089] From the viewpoint of high frequency characteristics, adhesion to a conductor, and flame retardancy, the phosphate ester flame retardant (A) is preferably a compound represented by the following general formula (A-1).

[0090] [Chemical formula 6]

[0091]

[0092] (Where R a1 ~R a4 Each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. a1 It represents a divalent group represented by the following general formula (A-2) or a divalent condensed polycyclic aromatic hydrocarbon group containing two or more aromatic ring structures. a1 ~n a4 Each independently represents an integer from 0 to 5, and n a5 Indicates an integer from 1 to 5. )

[0093] [Chemical formula 7]

[0094]

[0095] (Where R a5 and R a6 Each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. a2 represents an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a thioether group, a sulfonyl group, a carbonyloxy group, a keto group, or a single bond. a6 and n a7 Each independently represents an integer from 0 to 4. a8 Indicates an integer from 1 to 3. )

[0096] As R in the above general formula (A-1) a1 ~R a4 The aliphatic hydrocarbon group having 1 to 5 carbon atoms shown in the above formula includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, etc. As the aliphatic hydrocarbon group, an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferred, an alkyl group having 1 to 3 carbon atoms is more preferred, and a methyl group is further preferred.

[0097] n a1 ~n a4It is preferably an integer of 0 to 2, and more preferably 0 or 2. a1 ~n a4 When the integer is 2 or more, multiple R a1 Each other, R a2 Each other, R a3 Each other or R a4 They may be the same as or different from each other.

[0098] n a5 represents an integer of 1 to 5, preferably an integer of 1 to 3, more preferably 1 or 2, and further preferably 1. a5 When the number of X is an integer greater than 2, a1 Each other and multiple n a4 They may be the same as or different from each other.

[0099] Regarding R in the above general formula (A-2): a5 and R a6 The description of the aliphatic hydrocarbon group having 1 to 5 carbon atoms is similar to that of R in the above general formula (A-1). a1 ~R a4 The same applies to the description of the aliphatic hydrocarbon group having 1 to 5 carbon atoms.

[0100] n a6 and n a7 represents an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0. a6 or a7 When the integer is 2 or more, multiple R a5 Each other or multiple R a6 They may be the same as or different from each other.

[0101] As X a2 Examples of the alkylene group having 1 to 5 carbon atoms include methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, and 1,5-pentylene.

[0102] As X a2 Examples of the alkylidene group having 2 to 5 carbon atoms include ethylidene, propylidene, isopropylidene, butylidene, isobutylidene, pentylidene and isopentylidene.

[0103] X a2 Among the groups shown, from the viewpoints of high-frequency characteristics, adhesion to a conductor, and flame retardancy, a methylene group, an isopropylidene group, and a single bond are preferred, and a single bond is more preferred.

[0104] From the perspective of high frequency characteristics, adhesion to conductors and flame retardancy, X a2It is preferably a divalent group represented by the following formula (A-2-1) or a divalent group represented by the following formula (A-2-2), and more preferably a divalent group represented by the following formula (A-2-2).

[0105] [Chemical formula 8]

[0106]

[0107] In the above general formula (A-2), n a8 represents an integer of 1 to 3, preferably 1 or 2, more preferably 1. a8 When the number of X is an integer greater than 2, a2 Each other and multiple n a7 They may be the same as or different from each other.

[0108] As X in the above general formula (A-1) a1 The divalent fused polycyclic aromatic hydrocarbon group containing two or more aromatic ring structures shown in the figure may be a divalent group formed by removing two hydrogen atoms from a fused polycyclic aromatic hydrocarbon such as naphthalene, anthracene, pyrene, etc. These fused polycyclic aromatic hydrocarbon groups may or may not be substituted by a substituent. As a substituent of the fused polycyclic aromatic hydrocarbon group, an aliphatic hydrocarbon group having 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, etc.; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. may be mentioned.

[0109] Examples of the phosphate flame retardant (A) include 4,4'-biphenol-diphenyl phosphate, bisphenol A-diphenyl phosphate, 4,4'-biphenol-bis(cresyl phosphate), bisphenol A-bis(cresyl phosphate), 4,4'-biphenol-bis(2,6-xylyl phosphate), bisphenol A-bis(2,6-xylyl phosphate), 4,4'-biphenol-polyphenyl phosphate, bisphenol A-polyphenyl phosphate, 4,4'-biphenol-polycresyl phosphate, bisphenol A-polycresyl phosphate, 4,4'-biphenol-poly(2,6-xylyl phosphate), and bisphenol A-poly(2,6-xylyl phosphate). Among them, 4,4'-biphenol-bis(2,6-xylyl phosphate) is preferred from the viewpoints of high frequency characteristics, adhesion to conductors, and flame retardancy.

[0110] It should be noted that the "poly" in the above-mentioned exemplary compounds refers to a repeating unit composed of a structure derived from a dihydric phenol compound constituting a phosphate ester compound and a structure derived from phosphoric acid (for example, in the above-mentioned general formula (A-1), n a5 A compound having a structural unit number (i.e., the number of structural units) of 2 or more may also refer to a compound in which the average value of the above-mentioned repeating units exceeds 1 due to the inclusion of this compound.

[0111] The average particle size of the phosphate flame retardant (A) is not particularly limited, but is preferably 0.1 to 10 μm, more preferably 0.3 to 5 μm, further preferably 0.5 to 3 μm, and particularly preferably 0.8 to 2.5 μm. If the average particle size of the phosphate flame retardant (A) is above the lower limit, excellent handling properties tend to be obtained, and if it is below the upper limit, the dispersibility of the component (A) in the resin composition becomes good, and excellent flame retardancy tends to be obtained.

[0112] Here, the average particle size in this embodiment refers to the particle size corresponding to the point of 50% volume when the cumulative frequency distribution curve based on the particle size is obtained with the total volume of the particles being 100%. The average particle size can be measured by a particle size distribution measuring device using a laser diffraction scattering method.

[0113] The average particle size of the phosphate ester flame retardant (A) can be adjusted to the above range by applying a known dry or wet pulverization method.

[0114] The melting point of the phosphate flame retardant (A) is not particularly limited, but is preferably 50 to 250° C., more preferably 100 to 230° C., further preferably 150 to 200° C., and particularly preferably 170 to 190° C. If the melting point of the phosphate flame retardant (A) is above the lower limit, excellent dielectric properties tend to be obtained due to the high crystallinity of the component (A), while if it is below the upper limit, the component (A) melts during heat curing of the resin composition, thereby improving dispersibility and thereby obtaining excellent flame retardancy.

[0115] In addition, the melting point can be measured using a differential scanning calorimetry (DSC measurement) apparatus.

[0116] (Content of component (A))

[0117] The content of phosphorus atoms from the phosphate flame retardant (A) in the resin composition of the present embodiment is not particularly limited, and is preferably 0.2 to 5% by mass, more preferably 0.3 to 3% by mass, further preferably 0.6 to 2.5% by mass, further preferably 1.0 to 2.2% by mass, and particularly preferably 1.2 to 2.0% by mass in the solid content of the resin composition excluding the inorganic filler. If the content of the component (A) is above the lower limit, there is a tendency to obtain better flame retardancy while suppressing the deterioration of high-frequency characteristics, and if it is below the upper limit, there is a tendency to obtain better formability, adhesion to the conductor, better heat resistance and high-frequency characteristics.

[0118] In the present embodiment, the "resin component" is defined as all components in the solid content constituting the resin composition except inorganic compounds such as inorganic fillers described below, flame retardants such as the component (A), and flame retardant aids.

[0119] In addition, the solid content in this embodiment refers to the components in the resin composition excluding volatile substances such as water and solvents described later. That is, the solid content also includes substances that are liquid, syrupy or waxy at room temperature around 25°C, and does not necessarily mean solid.

[0120] In addition, the content of the phosphate-based flame retardant (A) in the resin composition of the present embodiment is not particularly limited, but from the same viewpoint as above, it is preferably 3 to 50 parts by mass, more preferably 5 to 45 parts by mass, further preferably 10 to 40 parts by mass, further preferably 15 to 35 parts by mass, and particularly preferably 20 to 30 parts by mass, relative to 100 parts by mass of the total resin component.

[0121] <Polyphenylene ether derivative (B)>

[0122] The polyphenylene ether derivative (B) is a polyphenylene ether derivative having an ethylenically unsaturated bond-containing group at both terminals.

[0123] It should be noted that, in the present specification, the "group containing an ethylenically unsaturated bond" refers to a substituent containing a carbon-carbon double bond capable of an addition reaction, and does not include double bonds of an aromatic ring.

[0124] The polyphenylene ether derivative (B) may be used alone or in combination of two or more.

[0125] As the group containing ethylenically unsaturated bonds, unsaturated aliphatic hydrocarbon groups such as vinyl, allyl, 1-methylallyl, isopropenyl, 2-butenyl, 3-butenyl, and styryl can be cited; maleimide groups, groups represented by the following general formula (B-1), and the like, groups containing heteroatoms and ethylenically unsaturated bonds, etc. Among them, from the viewpoints of high-frequency characteristics, adhesion to conductors, and flame retardancy, the group represented by the following general formula (B-1) is preferred.

[0126] [Chemical formula 9]

[0127]

[0128] (Where R b1 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. )

[0129] R b1 The alkyl group having 1 to 20 carbon atoms may be any of a linear alkyl group, a branched alkyl group, and a cyclic alkyl group, and is preferably a linear alkyl group.

[0130] The alkyl group has preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, further preferably 1 to 3 carbon atoms, and particularly preferably 1 carbon atom.

[0131] Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, pentadecyl, hexadecyl, and heptadecyl groups. Among them, a methyl group is preferred.

[0132] From the viewpoint of high frequency characteristics, adhesion to conductors and flame retardancy, the group represented by the general formula (B-1) is preferably a (meth)acryloyl group (i.e., R in the general formula (B-1) b1 It should be noted that in the present embodiment, "(meth)acryloyl group" means acryloyl group or methacryloyl group.

[0133] It should be noted that in the present specification, groups that have an unsaturated aliphatic hydrocarbon group in part, such as a maleimide group and the group represented by the above general formula (B-1), but cannot be called an unsaturated aliphatic hydrocarbon group when the group as a whole is viewed are not included in the above-mentioned "unsaturated aliphatic hydrocarbon group".

[0134] The polyphenylene ether derivative (B) preferably has a group represented by the above-mentioned general formula (B-1) at one or both ends.

[0135] The number of ethylenically unsaturated bond-containing groups in one molecule of the polyphenylene ether derivative (B) is not particularly limited, but is preferably 2 to 5, more preferably 2 to 3, and still more preferably 2. When the number of ethylenically unsaturated bond-containing groups is at least the lower limit, excellent heat resistance tends to be obtained, while when it is at most the upper limit, excellent fluidity and moldability tend to be obtained.

[0136] The polyphenylene ether derivative (B) may have an ethylenically unsaturated bond-containing group at both terminals, and may have an ethylenically unsaturated bond-containing group other than the two terminals, but preferably has an ethylenically unsaturated bond-containing group only at the two terminals. The polyphenylene ether derivative (B) is preferably a polyphenylene ether having methacryloyl groups at both terminals.

[0137] The polyphenylene ether derivative (B) has a phenylene ether bond, and preferably has a structural unit represented by the following general formula (B-2).

[0138] [Chemical formula 10]

[0139]

[0140] (Where R b2 represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. b1 Indicates an integer from 0 to 4. )

[0141] As R in the above general formula (B-2) b2 The aliphatic hydrocarbon group having 1 to 5 carbon atoms shown in the above formula includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, etc. As the aliphatic hydrocarbon group, an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferred, an alkyl group having 1 to 3 carbon atoms is more preferred, and a methyl group is further preferred.

[0142] n b1 represents an integer of 0 to 4, preferably 1 or 2, more preferably 2. It should be noted that in n b1 When R is 1 or 2, b2 Preferably, the substitution is at the ortho position on the benzene ring (wherein the substitution position of the oxygen atom is taken as the reference). b1 When the integer is 2 or more, multiple R b2 They can be the same or different from each other.

[0143] The structural unit represented by the general formula (B-2) is preferably a structural unit represented by the following general formula (B-2').

[0144] [Chemical formula 11]

[0145]

[0146] From the viewpoint of high-frequency characteristics, adhesion to a conductor, and flame retardancy, the polyphenylene ether derivative (B) is preferably a compound represented by the following general formula (B-3).

[0147] [Chemical formula 12]

[0148]

[0149] (Where R b2 and n b1 As described in the above general formula (B-2). b3 and R b4 Each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. b2 and n b3 Each independently represents an integer from 0 to 4. b4 and n b5 Each independently represents an integer from 0 to 20, and n b4 and n b5 The total of is an integer from 1 to 30. b1 Y represents an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a thioether group, a sulfonyl group, a carbonyloxy group, a keto group or a single bond. b1 and Y b2 Each independently represents the above-mentioned ethylenically unsaturated bond-containing group. )

[0150] Regarding R in the above general formula (B-3): b3 and R b4 The description of the aliphatic hydrocarbon group having 1 to 5 carbon atoms is similar to that of R in the above general formula (B-2). b2 The same applies to the description of the aliphatic hydrocarbon group having 1 to 5 carbon atoms.

[0151] n b2 and n b3 represents an integer of 0 to 4, preferably an integer of 0 to 3, preferably 2 or 3. b2 or b3 When the integer is 2 or more, multiple R b3 Each other or multiple R b4 They can be the same or different from each other.

[0152] n b4 and n b5 represents an integer of 0 to 20, preferably an integer of 1 to 20, more preferably an integer of 2 to 15, and further preferably an integer of 3 to 10. b4 or b5 When n is an integer greater than 2, multiple n b1 They may be the same as or different from each other.

[0153] n b4 and n b5 The total of is an integer of 1-30, preferably an integer of 2-25, more preferably an integer of 5-20, and further preferably an integer of 7-15.

[0154] As X in the above general formula (B-3) b1 Examples of the alkylene group having 1 to 5 carbon atoms include methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, and 1,5-pentylene.

[0155] As X b1 Examples of the alkylidene group having 2 to 5 carbon atoms include ethylidene, propylidene, isopropylidene, butylidene, isobutylidene, pentylidene and isopentylidene.

[0156] In X b1 Among the groups shown, an isopropylidene group is preferred from the viewpoints of high-frequency characteristics, adhesion to a conductor, and flame retardancy.

[0157] About Y b1 and Y b2 Preferred embodiments of the ethylenically unsaturated bond-containing group are as described above.

[0158] From the viewpoint of high frequency characteristics, adhesion to a conductor, and flame retardancy, the compound represented by the general formula (B-3) is preferably a compound represented by the following general formula (B-4).

[0159] [Chemical formula 13]

[0160]

[0161] (where n b4 and n b5 As shown in the above description of general formula (B-3). b5 and R b6 Each independently represents a hydrogen atom or a methyl group. b2 represents a methylene or isopropylidene group. )

[0162] [Weight average molecular weight (Mw) of polyphenylene ether derivative (B)]

[0163] The weight average molecular weight (Mw) of the polyphenylene ether derivative (B) is not particularly limited, but is preferably 500 to 7000, more preferably 800 to 5000, further preferably 1000 to 3000, and particularly preferably 1200 to 2500. When the weight average molecular weight (Mw) of the component (B) is at least the above lower limit, a cured product having excellent dielectric properties of polyphenylene ether and excellent heat resistance tends to be obtained, while when it is at most the above upper limit, excellent moldability tends to be obtained.

[0164] In addition, in this specification, the weight average molecular weight is a value converted from a calibration curve using standard polystyrene by gel permeation chromatography (GPC), and more specifically, a value determined by the measurement method described in the Examples.

[0165] The synthesis method of the polyphenylene ether derivative (B) can be applied to a known synthesis method and modification method of polyphenylene ether, and is not particularly limited.

[0166] (Content of component (B))

[0167] The content of the polyphenylene ether derivative (B) in the resin composition of the present embodiment is not particularly limited, and is preferably 5 to 80 parts by mass, more preferably 6 to 45 parts by mass, further preferably 7 to 30 parts by mass, and particularly preferably 8 to 20 parts by mass, relative to 100 parts by mass of the total resin component. If the content of the component (B) is above the lower limit, there is a tendency to obtain more excellent high-frequency characteristics and low hygroscopicity, and if it is below the upper limit, there is a tendency to obtain excellent heat resistance, formability and processability.

[0168] <Thermosetting resin (C)>

[0169] The resin composition of the present embodiment preferably further contains one or more thermosetting resins (C) selected from epoxy resins, cyanate resins, and maleimide compounds. Among them, maleimide compounds are preferably contained from the viewpoints of high-frequency characteristics, adhesion to conductors, and flame retardancy.

[0170] The thermosetting resin (C) may be used alone or in combination of two or more.

[0171] (Epoxy resin)

[0172] As the epoxy resin, an epoxy resin having two or more epoxy groups in one molecule is preferred. Here, epoxy resins are classified into glycidyl ether type epoxy resins, glycidyl amine type epoxy resins, glycidyl ester type epoxy resins, etc. Among them, glycidyl ether type epoxy resins are preferred.

[0173] Epoxy resins are classified into various types of epoxy resins according to the difference of the main skeleton. Among the above-mentioned various types of epoxy resins, they are further classified into bisphenol-type epoxy resins such as bisphenol A epoxy resin, bisphenol F epoxy resin, and bisphenol S epoxy resin; alicyclic epoxy resins; aliphatic chain epoxy resins; phenolic epoxy resins such as phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F novolac type epoxy resin, phenol aralkyl novolac type epoxy resin, and biphenyl aralkyl novolac type epoxy resin; stilbene type epoxy resin; dicyclopentadiene type epoxy resin; naphthol novolac type epoxy resin, naphthol aralkyl type epoxy resin and other naphthalene skeleton-containing epoxy resins; biphenyl type epoxy resin; xylene type epoxy resin; dihydroanthracene type epoxy resin; dicyclopentadiene type epoxy resin, etc.

[0174] When an epoxy resin is used, a curing agent, a curing aid, and the like for the epoxy resin may be used in combination as necessary.

[0175] (Cyanate ester resin)

[0176] Examples of the cyanate resin include 2,2-bis(4-cyanophenyl)propane, bis(4-cyanophenyl)ethane, bis(3,5-dimethyl-4-cyanophenyl)methane, 2,2-bis(4-cyanophenyl)-1,1,1,3,3,3-hexafluoropropane, α,α'bis(4-cyanophenyl)-m-diisopropylbenzene, cyanate compounds of phenol-added dicyclopentadiene polymers, phenol novolac-type cyanate compounds, cresol novolac-type cyanate compounds, and the like.

[0177] When a cyanate ester resin is used, a curing agent, a curing aid, and the like for the cyanate ester resin may be used in combination as necessary.

[0178] (Maleimide compound)

[0179] The maleimide compound is preferably at least one selected from maleimide compounds having two or more N-substituted maleimide groups [hereinafter, sometimes simply referred to as “maleimide compound (c1)” or “component (c1)”] and derivatives thereof.

[0180] In addition, as said "its derivative", addition products of the maleimide compound which has two or more N-substituted maleimide groups and the amine compound, such as the diamine compound mentioned later, etc. are mentioned.

[0181] Specific examples of maleimide compounds (c1) are not particularly limited as long as they are maleimide compounds having two or more N-substituted maleimide groups, and include aromatic maleimide compounds such as bis(4-maleimidephenyl)methane, polyphenylmethane maleimide, bis(4-maleimidephenyl)ether, bis(4-maleimidephenyl)sulfone, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, meta-phenylene bismaleimide, and 2,2-bis[4-(4-maleimidephenoxy)phenyl]propane; and aliphatic maleimide compounds such as 1,6-bismaleimide-(2,2,4-trimethyl)hexane and pyrophosphate binder-type long-chain alkyl bismaleimide. Among them, from the viewpoint of adhesion to the conductor and mechanical properties, aromatic maleimide compounds are preferred, aromatic bismaleimide compounds are more preferred, and 2,2-bis[4-(4-maleimidephenoxy)phenyl]propane and 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide are further preferred.

[0182] As the maleimide compound (c1), a compound represented by the following general formula (C1-1) is preferred.

[0183] [Chemical formula 14]

[0184]

[0185] (Where X c1 represents a divalent organic group. )

[0186] As X in the above general formula (C1-1) c1 The divalent organic group represented by may be a group represented by the following general formula (C1-2), (C1-3), (C1-4) or (C1-5).

[0187] [Chemical formula 15]

[0188]

[0189] (Where R c1represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. c1 Indicates an integer from 0 to 4. )

[0190] As R c1 Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, etc. The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and more preferably a methyl group.

[0191] n c1 represents an integer of 0 to 4, and is preferably an integer of 0 to 2, and more preferably 0, from the viewpoint of easy availability. c1 When the integer is 2 or more, multiple R c1 They can be the same or different from each other.

[0192] [Chemical formula 16]

[0193]

[0194] (Where R c2 and R c3 Each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. c2 It represents an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a thioether 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 independently represents an integer from 0 to 4. )

[0195] About R c2 and R c3 The description of the aliphatic hydrocarbon group having 1 to 5 carbon atoms is similar to that of R in the above general formula (C1-2). c1 The same applies to the description of the aliphatic hydrocarbon group having 1 to 5 carbon atoms.

[0196] As X c2 Examples of the alkylene group having 1 to 5 carbon atoms include methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, etc. The alkylene group is preferably an alkylene group having 1 to 3 carbon atoms, and more preferably a methylene group.

[0197] As X c2 Examples of the alkylidene group having 2 to 5 carbon atoms include ethylidene, propylidene, isopropylidene, butylidene, isobutylidene, pentylidene, and isopentylidene. The alkylidene group is preferably isopropylidene.

[0198] n c2 and n c3represents an integer of 0 to 4, and is preferably an integer of 0 to 2, and more preferably 0 or 2, from the viewpoint of easy availability. c2 or c3 When the integer is 2 or more, multiple R c2 Each other or multiple R c3 They may be the same as or different from each other.

[0199] X c2 The divalent group represented by the general formula (C1-3-1) is as follows.

[0200] [Chemical formula 17]

[0201]

[0202] (Where R c4 and R c5 Each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. c3 represents an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a thioether group, a sulfonyl group, a carbonyloxy group, a keto group, or a single bond. c4 and n c5 Each independently represents an integer from 0 to 4. )

[0203] About R c4 and R c5 The description of the aliphatic hydrocarbon group having 1 to 5 carbon atoms is similar to that of R in the above general formula (C1-2). c1 The same applies to the description of the aliphatic hydrocarbon group having 1 to 5 carbon atoms.

[0204] As X c3 The alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms shown in the formula (C1-3) include the following: c2 The alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms are the same groups. Among them, the isopropylidene group is preferred from the viewpoints of high frequency characteristics, adhesion to a conductor, heat resistance, glass transition temperature, thermal expansion coefficient and flame retardancy.

[0205] X c3 Among the groups shown, an alkylidene group having 2 to 5 carbon atoms is preferred, and an isopropylidene group is more preferred.

[0206] n c4 and n c5 represents an integer of 0 to 4, and is preferably an integer of 0 to 2, and more preferably 0, from the viewpoint of easy availability. c4 or c5 When the integer is 2 or more, multiple R c4 Each other or multiple R c5They may be the same as or different from each other.

[0207] [Chemical formula 18]

[0208]

[0209] (where n c6 Indicates an integer from 1 to 10. )

[0210] From the perspective of ease of acquisition, n c6 It is preferably an integer of 1-5, and more preferably an integer of 1-3.

[0211] [Chemical formula 19]

[0212]

[0213] (Where R c6 and R c7 Each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. c7 Indicates an integer from 1 to 8. )

[0214] About R c6 and R c7 The description of the aliphatic hydrocarbon group having 1 to 5 carbon atoms is similar to that of R in the above general formula (C1-2). c1 The same applies to the description of the aliphatic hydrocarbon group having 1 to 5 carbon atoms.

[0215] n c7 It represents an integer of 1 to 8, preferably an integer of 1 to 3, and more preferably 1.

[0216] In n c7 When the integer is 2 or more, multiple R c6 Each other or multiple R c7 They may be the same as or different from each other.

[0217] As X in the above general formula (C1-1) c1 From the viewpoint of high frequency characteristics, it is preferably the following formula (X c1 -1)~(X c1 -3) is a divalent group represented by any of the following formula (X c1 -3) a divalent group.

[0218] [Chemical formula 20]

[0219]

[0220] (The wavy line indicates the bonding position to the nitrogen atom in the maleimide group.)

[0221] As the maleimide compound, a derivative of the maleimide compound (c1) is preferred from the viewpoints of solubility in an organic solvent, compatibility, adhesion to a conductor, and high-frequency characteristics.

[0222] The derivative of the maleimide compound (c1) is preferably a modified maleimide compound [hereinafter, sometimes referred to as “modified maleimide compound (X)” or “component (X)”] having a structural unit derived from the maleimide compound (c1) and a structural unit derived from an amine compound having a primary amino group [hereinafter, sometimes referred to as “component (c2)”].

[0223] In addition, the structural unit derived from the component (c1) and the structural unit derived from the component (c2) contained in the modified maleimide compound (X) may be one type each, or a combination of two or more types.

[0224] The modified maleimide compound (X) is preferably a compound having a structure represented by the following formula (C-1) obtained by addition reaction of the maleimide group of the component (c1) and the primary amino group of the component (c2).

[0225] [Chemical formula 21]

[0226]

[0227] (*Indicates bonding position to other structures.)

[0228] Examples of the structural unit derived from the component (c1) include one or more selected from the group consisting of a group represented by the following general formula (C1-6) and a group represented by the following general formula (C1-7).

[0229] [Chemical formula 22]

[0230]

[0231] (Where X c1 and X in the above general formula (C1-1) c1 Same as above, * indicates the bonding position with other structures. )

[0232] The content of the structural unit derived from the 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 further preferably 85 to 90% by mass. If the content of the structural unit derived from the component (c1) is within the above range, high-frequency characteristics become better and there is a tendency to obtain good film handling properties.

[0233] The amine compound (c2) is preferably a compound having two or more amino groups, and more preferably a diamine compound having two amino groups.

[0234] Examples of the amine compound (c2) include 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ketone, 4,4'-diaminobiphenyl, 3,3'-dimethyl 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( 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- Aromatic diamine compounds such as 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.

[0235] Among them, as the component (c2), 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4,4'-[1,3-phenylenebis(1-methylethylidene)]dianiline, and 4,4'-[1,4-phenylenebis(1-methylethylidene)]dianiline are preferred from the viewpoints of excellent high-frequency characteristics and low water absorption. In addition, 3,3'-dimethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane is preferred from the viewpoints of excellent mechanical characteristics such as high adhesion to conductors, elongation, and breaking strength. 2,2-bis[4-(4-aminophenoxy)phenyl]propane is preferred. In addition, from the viewpoints of excellent solubility in organic solvents, reactivity during synthesis, heat resistance, high adhesion to conductors, high frequency characteristics and low hygroscopicity, 4,4'-[1,3-phenylenebis(1-methylethylidene)]dianiline and 4,4'-[1,4-phenylenebis(1-methylethylidene)]dianiline are preferred. In addition, from the viewpoint of low thermal expansion, amine-modified siloxane compounds are preferred.

[0236] As the amine compound (c2), a compound represented by the following general formula (C2-1) is preferred.

[0237] [Chemical formula 23]

[0238] H2N-X c4 -NH2 (C2-1)

[0239] (Where X c4 represents a divalent organic group. )

[0240] The component (c2) preferably contains X in the above general formula (C2-1): c4 An aromatic diamine compound having a divalent group represented by the following general formula (C2-2) [hereinafter, sometimes simply referred to as "aromatic diamine compound (C2-2)"]. ].

[0241] [Chemical formula 24]

[0242]

[0243] (Where R c11 and R c12 Each 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. c5It represents an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a thioether group, a sulfonyl group, a carbonyloxy group, a keto group, a fluorenylene group, a single bond, or a divalent group represented by the following general formula (C2-2-1) or (C2-2-2). c8 and n c9 Each independently represents an integer from 0 to 4. )

[0244] As R in the above general formula (C2-2) c11 and R c12 Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl and n-pentyl.

[0245] As X c5 Examples of the alkylene group having 1 to 5 carbon atoms include methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, and 1,5-pentylene.

[0246] As X c5 Examples of the alkylidene group having 2 to 5 carbon atoms include ethylidene, propylidene, isopropylidene, butylidene, isobutylidene, pentylidene and isopentylidene.

[0247] n c8 and n c9 represents an integer of 0 to 4, and is preferably 0 or 1 from the viewpoint of easy availability. c8 or c9 When the integer is 2 or more, multiple R c11 Each other or multiple R c12 They may be the same as or different from each other.

[0248] X in the above general formula (C2-2) c5 The divalent groups represented by the general formula (C2-2-1) are as follows.

[0249] [Chemical formula 25]

[0250]

[0251] (Where R c13 and R c14 Each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. Xc6 represents an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, a m-phenylene diisopropylidene group, a p-phenylene diisopropylidene group, an ether group, a thioether group, a sulfonyl group, a carbonyloxy group, a keto group or a single bond. c10 and n c11 Each independently represents an integer from 0 to 4. )

[0252] Regarding R in the above general formula (C2-2-1):c13 and R c14 The description of the aliphatic hydrocarbon group having 1 to 5 carbon atoms is similar to that of R in the above general formula (C2-2). c11 and R c12 The same applies to the description of the aliphatic hydrocarbon group having 1 to 5 carbon atoms.

[0253] About X c6 The description of the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms is the same as that of X in the above general formula (C2-2). c5 The descriptions of the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms are the same.

[0254] n c10 and n c11 represents an integer of 0 to 4, and is preferably an integer of 0 to 2, and more preferably 0, from the viewpoint of easy availability. c10 or c11 When the integer is 2 or more, multiple R c13 Each other or multiple R c14 They may be the same as or different from each other.

[0255] X in the above general formula (C2-2) c5 The divalent group represented by the general formula (C2-2-2) is as follows.

[0256] [Chemical formula 26]

[0257]

[0258] (Where R c15 represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. c7 and X c8 Each independently represents an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a thioether group, a sulfonyl group, a carbonyloxy group, a keto group or a single bond. c12 Indicates an integer from 0 to 4. )

[0259] Regarding R in the above general formula (C2-2-2): c15 The description of the aliphatic hydrocarbon group having 1 to 5 carbon atoms is similar to that of R in the above general formula (C2-2). c11 and R c12 The same applies to the description of the aliphatic hydrocarbon group having 1 to 5 carbon atoms.

[0260] As X c7 and X c8 The alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms shown in the formula (C2-2) are exemplified by the following: c5The alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms are the same groups. c7 and X c8 , preferably an alkylidene group having 2 to 5 carbon atoms, more preferably an isopropylidene group.

[0261] n c12 represents an integer of 0 to 4, and is preferably an integer of 0 to 2, and more preferably 0, from the viewpoint of easy availability. c12 When the integer is 2 or more, multiple R c15 They can be the same or different from each other.

[0262] In addition, the component (c2) preferably contains X in the general formula (C2-1) c4 It is an amine-modified siloxane compound having a divalent group containing a structural unit represented by the following general formula (C2-3), and more preferably containing X in the above general formula (C2-1): c4 A siloxane compound having amines at both ends and having a divalent group represented by the following general formula (C2-4) [hereinafter, sometimes simply referred to as a "siloxane compound (C2-4) having amines at both ends".].

[0263] [Chemical formula 27]

[0264]

[0265] (Where R c16 and R c17 Each independently represents an alkyl group having 1 to 5 carbon atoms, a phenyl group or a substituted phenyl group.

[0266] [Chemical formula 28]

[0267]

[0268] (Where R c16 and R c17 and R in the above general formula (C2-3) c16 and R c17 Same, R c18 and R c19 Each 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 Indicates an integer from 2 to 100. )

[0269] As R in the above general formulas (C2-3) and (C2-4) c16 ~R c19Examples of the alkyl group having 1 to 5 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, etc. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group.

[0270] As R c16 ~R c19 The substituent of the phenyl group in the substituted phenyl group shown in the figure may be an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkynyl group having 2 to 5 carbon atoms, etc. Examples of the alkyl group having 1 to 5 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, etc. Examples of the alkenyl group having 2 to 5 carbon atoms include vinyl, allyl, etc. Examples of the alkynyl group having 2 to 5 carbon atoms include ethynyl, propargyl, etc.

[0271] As X c9 and X c10 The divalent organic group shown in the formula (a) may include an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -O-, or a divalent linking group formed by combining these groups. Examples of the alkylene group include alkylene groups having 1 to 10 carbon atoms, such as methylene, ethylene, and propylene. Examples of the alkenylene group include alkenylene groups having 2 to 10 carbon atoms. Examples of the alkynylene group include alkynylene groups having 2 to 10 carbon atoms. Examples of the arylene group include arylene groups having 6 to 20 carbon atoms, such as phenylene and naphthylene.

[0272] Among them, as X c9 and X c10 , preferably an alkylene group and an arylene group, and more preferably an alkylene group.

[0273] n c13 represents an integer of 2 to 100, preferably an integer of 2 to 50, more preferably an integer of 3 to 40, and further preferably an integer of 5 to 30. c13 When the integer is 2 or more, multiple R c16 Each other or multiple R c17 They may be the same as or different from each other.

[0274] The functional group equivalent of the amine-modified siloxane compound is not particularly limited, but is preferably 300 to 3000 g / mol, more preferably 400 to 2000 g / mol, and further preferably 600 to 1000 g / mol.

[0275] As component (c2), from the viewpoint of heat resistance and low thermal expansion, it is preferred to use an aromatic diamine compound and an amine-modified siloxane compound in combination, and it is more preferred to use the aromatic diamine compound (C2-2) and the dual-end amine-modified siloxane compound (C2-4) in combination.

[0276] The usage ratio (content ratio as structural units) of the aromatic diamine compound and the amine-modified siloxane compound [aromatic diamine compound / amine-modified siloxane compound] is not particularly limited, but is preferably 20 / 80 to 80 / 20, more preferably 40 / 60 to 70 / 30, and further preferably 50 / 50 to 65 / 35 in terms of mass ratio.

[0277] Examples of the structural unit derived from the component (c2) include one or more selected from the group consisting of a group represented by the following general formula (C2-5) and a group represented by the following general formula (C2-6).

[0278] [Chemical formula 29]

[0279]

[0280] (Where X c4 and X in the above general formula (C2-1) c4 Same as above, * indicates the bonding position with other structures. )

[0281] The content of the structural unit derived from the 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 further preferably 10 to 15% by mass. If the content of the structural unit derived from the component (c2) is within the above range, high-frequency characteristics are excellent, and better heat resistance, flame retardancy, and glass transition temperature tend to be obtained.

[0282] The total content of the structural units derived from the component (c1) and the structural units derived from the 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, further preferably 95% by mass or more, and particularly preferably 100% by mass (i.e., consisting only of structural units derived from the component (c1) and structural units derived from the component (c2)).

[0283] The content ratio of the structural unit derived from the component (c1) to the structural unit derived from the component (c2) in the modified maleimide compound (X) is not particularly limited, and the equivalent ratio (Ta1 / Ta2) of the total equivalent weight (Ta1) of the groups derived from the maleimide group (including the maleimide group) of the component (c1) to the total equivalent weight (Ta2) of the groups derived from the -NH2 group (including -NH2) of the component (c2) is preferably 0.05 to 10, more preferably 1 to 5. When the equivalent ratio (Ta1 / Ta2) is within the above range, high-frequency characteristics are excellent, and better heat resistance, flame retardancy and glass transition temperature tend to be obtained.

[0284] From the viewpoints of high-frequency characteristics, solubility in organic solvents, high adhesion to conductors, moldability, and the like, the maleimide compound preferably contains a compound represented by the following general formula (C-2).

[0285] [Chemical formula 30]

[0286]

[0287] (Where X c1 and X c4 As described in the above general formulas (c1-1) and (c2-1).

[0288] (Method for producing modified maleimide compound (X))

[0289] The component (X) can be obtained as a reaction product of the component (c1) and the component (c2), and can be produced, for example, by reacting the component (c1) and the component (c2) in an organic solvent.

[0290] Specifically, a predetermined amount of component (c1), component (c2), and other components as needed are placed in a synthesis reactor, and component (c1) and component (c2) are subjected to a Michael addition reaction [hereinafter, sometimes referred to as "preliminary reaction"], thereby obtaining a modified maleimide compound (X).

[0291] The reaction conditions in the preliminary reaction are not particularly limited, but from the viewpoint of suppressing gelation and obtaining good reactivity and workability, the reaction temperature is preferably 50 to 160° C. and the reaction time is preferably 1 to 10 hours.

[0292] In the preliminary reaction, a reaction catalyst may be used as needed. Examples of the reaction catalyst include acidic catalysts such as p-toluenesulfonic acid; amines such as triethylamine, pyridine, and tributylamine; imidazoles such as methylimidazole and phenylimidazole; phosphorus-based catalysts such as triphenylphosphine, etc. They may be used alone or in combination of two or more. In addition, the amount of the reaction catalyst is not particularly limited, and is, for example, 0.01 to 5 parts by mass relative to 100 parts by mass of the total amount of component (c1) and component (c2).

[0293] In addition, in the pre-reaction, an organic solvent can be added as needed or concentrated to adjust the solid component concentration and solution viscosity of the reaction raw materials. The solid component concentration of the reaction raw materials is not particularly limited, preferably 10 to 90 mass %, more preferably 20 to 80 mass %. If the solid component concentration of the reaction raw materials is above the above-mentioned lower limit, sufficient reaction speed can be obtained, and the tendency to become favorable in terms of manufacturing cost is arranged, and if it is below the above-mentioned upper limit, better solubility, stirring efficiency, and the tendency to become good and difficult for gelation can be obtained.

[0294] 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, further preferably 1,500 to 4,000, and particularly preferably 2,000 to 3,000.

[0295] (Content of component (C))

[0296] When the resin composition of the present embodiment contains a thermosetting resin (C), the content thereof is not particularly limited, but from the viewpoint of high-frequency characteristics, heat resistance and formability, it is preferably 10 to 95 parts by mass, more preferably 30 to 90 parts by mass, further preferably 50 to 85 parts by mass, and particularly preferably 60 to 80 parts by mass, relative to 100 parts by mass of the total resin components.

[0297] When the resin composition of the present embodiment contains a thermosetting resin (C), the content ratio [(B) / (C)] of the polyphenylene ether derivative (B) to the thermosetting resin (C) is not particularly limited, and is preferably 5 / 95 to 80 / 20, more preferably 6 / 94 to 60 / 40, further preferably 8 / 92 to 40 / 60, and particularly preferably 10 / 90 to 20 / 80 in terms of mass ratio. If the content ratio [(B) / (C)] is above the lower limit, there is a tendency to obtain more excellent high-frequency characteristics and low hygroscopicity, and if it is below the upper limit, there is a tendency to obtain more excellent heat resistance, formability and processability.

[0298] The resin composition of the present embodiment preferably further contains one or more selected from the group consisting of a styrene-based thermoplastic elastomer (D), a curing accelerator (E), and an inorganic filler (F). Next, each of these components will be described.

[0299] <Styrene-based thermoplastic elastomer (D)>

[0300] The resin composition of the present embodiment tends to have a good balance among high-frequency characteristics, moldability, adhesion to a conductor, solder heat resistance, glass transition temperature, thermal expansion coefficient, and flame retardancy by containing the styrene-based thermoplastic elastomer (D).

[0301] The styrene-based thermoplastic elastomer (D) may be used alone or in combination of two or more.

[0302] Examples of the styrene-based thermoplastic elastomer (D) include thermoplastic elastomers having a structural unit derived from a styrene-based compound represented by the following general formula (D-1), preferably a thermoplastic elastomer having a structural unit derived from styrene (i.e., R d1 For hydrogen atoms, n d1A thermoplastic elastomer having a structural unit of 0.

[0303] [Chemical formula 31]

[0304]

[0305] (Where R d1 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R d2 It represents an alkyl group having 1 to 5 carbon atoms. d1 Indicates an integer from 0 to 5. )

[0306] As R d1 Examples of the alkyl group having 1 to 5 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and n-pentyl.

[0307] R d1 Among the groups shown, a hydrogen atom is preferred.

[0308] As R d2 Examples of the alkyl group having 1 to 5 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and n-pentyl. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group.

[0309] n dl It represents an integer of 0 to 5, preferably an integer of 0 to 2, and more preferably 0.

[0310] In n d1 When the integer is 2 or more, multiple R d1 They can be the same or different from each other.

[0311] Examples of the structural unit other than the structural unit derived from the styrene-based compound contained in the styrene-based thermoplastic elastomer (D) include a structural unit derived from butadiene, a structural unit derived from isoprene, a structural unit derived from maleic acid, and a structural unit derived from maleic anhydride.

[0312] The structural units derived from butadiene and the structural units derived from isoprene are preferably hydrogenated. In the case of hydrogenation, the structural units derived from butadiene become structural units of a mixture of ethylene units and butene units, and the structural units derived from isoprene become structural units of a mixture of ethylene units and propylene units.

[0313] Examples of the styrene-based thermoplastic elastomer (D) include hydrogenated products of styrene-butadiene-styrene block copolymers (SBS), hydrogenated products of styrene-isoprene-styrene block copolymers (SIS), etc. Among them, hydrogenated products of styrene-butadiene-styrene block copolymers (SBS) are preferred from the viewpoints of high-frequency characteristics, adhesion to conductors, heat resistance, glass transition temperature, and thermal expansion coefficient.

[0314] As hydrogenated products of styrene-butadiene-styrene block copolymers (SBS), there can be mentioned styrene-ethylene-butylene-styrene copolymers (SEBS) obtained by completely hydrogenating the carbon-carbon double bonds in the butadiene block, and styrene-butadiene-butylene-styrene (SBBS) obtained by partially hydrogenating the carbon-carbon double bonds at the 1,2-bonding site in the butadiene block. It should be noted that the complete hydrogenation in SEBS is usually 90% or more relative to the total carbon-carbon double bonds, can be 95% or more, can be 99% or more, and can be substantially 100%. In addition, the partial hydrogenation rate in SBBS is, for example, 60 to 85% relative to the total carbon-carbon double bonds.

[0315] In SEBS, the content of the structural unit derived from styrene [hereinafter sometimes referred to as "styrene content"] is not particularly limited, but is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, further preferably 15 to 60% by mass, and particularly preferably 20 to 50% by mass from the viewpoint of high-frequency characteristics, adhesion to a conductor, heat resistance, glass transition temperature, and thermal expansion coefficient.

[0316] The melt flow rate (MFR) of SEBS is not particularly limited, but is preferably 0.1 to 20 g / 10 min, more preferably 1 to 15 g / 10 min, further preferably 2 to 10 g / 10 min, and particularly preferably 3 to 7 g / 10 min under the measurement conditions of 230°C and a load of 2.16 kgf (21.2 N).

[0317] The styrene content in SBBS is not particularly limited, but is preferably 40 to 80% by mass, more preferably 50 to 75% by mass, and further preferably 55 to 75% by mass from the viewpoint of high-frequency characteristics, adhesion to a conductor, heat resistance, glass transition temperature, and thermal expansion coefficient.

[0318] The MFR of SBBS is not particularly limited, but is preferably 0.1 to 10 g / 10 min, more preferably 0.5 to 8 g / 10 min, and further preferably 1 to 6 g / 10 min under measurement conditions of 190° C. and a load of 2.16 kgf (21.2 N).

[0319] The styrene-based thermoplastic elastomer (D) may also be a thermoplastic elastomer obtained by acid modification using maleic anhydride, etc. The acid value of the acid-modified styrene-based thermoplastic elastomer (D) is not particularly limited, but is preferably 2 to 20 mgCH3ONa / g, more preferably 5 to 15 mgCH3ONa / g, and further preferably 7 to 13 mgCH3ONa / g.

[0320] (Content of component (D))

[0321] When the resin composition of the present embodiment contains a styrene-based thermoplastic elastomer (D), the content thereof is not particularly limited, and is preferably 2 to 60 parts by mass, more preferably 6 to 40 parts by mass, further preferably 10 to 30 parts by mass, and particularly preferably 12 to 20 parts by mass, relative to 100 parts by mass of the total resin component. If the content of the styrene-based thermoplastic elastomer (D) is above the lower limit, there is a tendency to obtain more excellent high-frequency characteristics and moisture absorption resistance, and if it is below the upper limit, there is a tendency to obtain good heat resistance, formability, processability, and flame retardancy.

[0322] <Curing Accelerator (E)>

[0323] The resin composition of the present embodiment contains a curing accelerator (E), whereby curability is improved, and more excellent high-frequency characteristics, heat resistance, adhesion to a conductor, elastic modulus, and glass transition temperature tend to be obtained.

[0324] When the resin composition of the present embodiment contains a curing accelerator (E), an appropriate curing accelerator (E) may be appropriately selected according to the type of the thermosetting resin (C) component to be used.

[0325] The curing accelerator (E) may be used alone or in combination of two or more.

[0326] Examples of the component (E) include amine curing accelerators, imidazole curing accelerators, phosphorus curing accelerators, organic metal salts, acidic catalysts, organic peroxides, etc. In this embodiment, the imidazole curing accelerator is not classified as an amine curing accelerator.

[0327] Examples of the amine-based curing accelerator include amine compounds having primary to tertiary amines, such as triethylamine, pyridine, tributylamine, and dicyandiamide; and quaternary ammonium compounds.

[0328] Examples of the imidazole curing accelerator include imidazole compounds such as methylimidazole, phenylimidazole, 2-undecylimidazole, and isocyanate-masked imidazole (for example, an addition product of a hexamethylene diisocyanate resin and 4-methyl-2-ethylimidazole).

[0329] Examples of the phosphorus-based curing accelerator include tertiary phosphines such as triphenylphosphine and quaternary phosphonium compounds such as tri-n-butylphosphine addition products of p-benzoquinone and the like.

[0330] Examples of the organic metal salt include carboxylates of manganese, cobalt, zinc, and the like.

[0331] Examples of the acidic catalyst include p-toluenesulfonic acid and the like.

[0332] Examples of the organic peroxide include diisopropyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyne-3, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, tert-butylperoxyisopropyl monocarbonate, and α,α′-di(tert-butylperoxy)diisopropylbenzene.

[0333] Among them, from the viewpoint of being able to obtain more excellent high frequency characteristics, heat resistance, adhesion to conductors, elastic modulus and glass transition temperature, preferably amine-based curing accelerators, imidazole-based curing accelerators, phosphorus-based curing accelerators, more preferably dicyandiamide, imidazole-based curing accelerators, quaternary phosphonium compounds, further preferably they are used in combination. At this point, organic peroxides can also be used in combination, but from the viewpoint of the physical properties of the cured product, preferably do not contain organic peroxides.

[0334] (Content of component (E))

[0335] When the resin composition of the present embodiment contains a curing accelerator (E), its content is not particularly limited, and is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, further preferably 0.1 to 3 parts by mass, and particularly preferably 0.5 to 2 parts by mass, relative to 100 parts by mass of the thermosetting resin (C). If the content of the curing accelerator (E) is within the above range, there is a tendency to obtain better high-frequency characteristics, heat resistance, storage stability and formability.

[0336] <Inorganic filler (F)>

[0337] The resin composition of the present embodiment tends to obtain more excellent low thermal expansion property, high elastic modulus property, heat resistance and flame retardancy by containing the inorganic filler (F).

[0338] The inorganic filler (F) may be used alone or in combination of two or more.

[0339] As inorganic filler (F), silica, alumina, titanium oxide, mica, beryllium oxide, 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 (sintered clay, etc.), talc, aluminum borate, silicon carbide, etc. can be cited. Among them, from the viewpoint of thermal expansion coefficient, elastic modulus, heat resistance and flame retardancy, silica, alumina, mica, talc are preferred, silica, alumina are more preferred, and silica is further preferred. As silica, for example, precipitated silica with high moisture content manufactured by wet method and dry method silica with almost no bound water, etc. manufactured by dry method can be cited. As dry method silica, crushed silica, fumed silica, fused silica (fused spherical silica), etc. can be cited according to the different manufacturing methods. Among them, fused spherical silica is preferred.

[0340] 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, further preferably 0.2 to 1 μm, and particularly preferably 0.3 to 0.8 μm.

[0341] When the resin composition of the present embodiment contains an inorganic filler (F), the content thereof is not particularly limited, but is preferably 10 to 250 parts by mass, more preferably 50 to 200 parts by mass, further preferably 80 to 180 parts by mass, further preferably 100 to 160 parts by mass, and particularly preferably 120 to 150 parts by mass, relative to 100 parts by mass of the total of the resin components.

[0342] When an inorganic filler (F) is used, a coupling agent may be used in combination as needed for the purpose of improving the dispersibility of the inorganic filler (F) and the adhesion of the inorganic filler (F) to the organic component in the resin composition. As the coupling agent, a silane coupling agent, a titanate coupling agent, etc. may be cited. One coupling agent may be used alone or two or more coupling agents may be used in combination.

[0343] When a coupling agent is used, the treatment method may be a so-called overall blending method in which the inorganic filler (F) is added after the inorganic filler (F) is mixed with the resin composition, and preferably, an inorganic filler that has been surface-treated with a coupling agent in a dry or wet manner is used. By adopting this method, the advantages of the inorganic filler (F) can be more effectively demonstrated.

[0344] In addition, the inorganic filler (F) may be used in the form of a slurry dispersed in an organic solvent in advance, as necessary.

[0345] <Other flame retardants, flame retardant additives, organic solvents>

[0346] The resin composition of the present embodiment may contain one or more selected from flame retardants (hereinafter, also referred to as "other flame retardants"), flame retardant aids and organic solvents other than component (A) as needed within the scope of not impairing the effect of the present invention. These components can be used alone or in combination of two or more. In addition, the resin composition of the present embodiment may not contain these components.

[0347] (Other flame retardants)

[0348] As other flame retardants, inorganic phosphorus flame retardants, organic phosphorus flame retardants (excluding component (A)), metal hydrates such as aluminum hydroxide hydrates and magnesium hydroxide hydrates, etc. It should be noted that metal hydroxides can also be equivalent to inorganic fillers, but in the case of materials that can impart flame retardancy, they are classified as flame retardants.

[0349] Examples of the inorganic phosphorus flame retardant include red phosphorus; ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate; inorganic nitrogen-containing phosphorus compounds such as phosphoric acid amide; phosphoric acid; and phosphine oxide.

[0350] As organic phosphorus flame retardants, aromatic phosphates, monosubstituted phosphonic acid diesters and disubstituted phosphinates other than component (A) can be cited; metal salts of disubstituted phosphinates, organic nitrogen-containing phosphorus compounds, cyclic organic phosphorus compounds, etc. Here, as "metal salts", lithium salts, sodium salts, potassium salts, calcium salts, magnesium salts, aluminum salts, titanium salts, zinc salts, etc. can be cited.

[0351] Examples of aromatic phosphates other than component (A) include aromatic phosphates represented by the following general formula (G-1), and examples of metal salts of di-substituted phosphinic acids include metal salts of di-substituted phosphinic acids represented by the following general formula (G-2).

[0352] [Chemical formula 32]

[0353]

[0354] (Where R g1 ~R g3 Each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. g1 and n g2 Each independently represents an integer from 0 to 5, and n g3 represents an integer from 0 to 4. g4 and R g5Each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms. M represents a lithium atom, a sodium atom, a potassium atom, a calcium atom, a magnesium atom, an aluminum atom, a titanium atom or a zinc atom. y represents an integer of 1 to 4.

[0355] As R in the above general formula (G-1) g1 ~R g3 Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl and n-pentyl.

[0356] In n g1 ~n g3 When the integer is 2 or more, multiple R g1 Each other, R g2 Each other or R g3 They may be the same as or different from each other.

[0357] As R in the above general formula (G-2) g4 and R g5 Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl and n-pentyl.

[0358] As R g4 and R g5 Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms include phenyl, naphthyl, biphenylyl, anthracenyl and the like.

[0359] y represents the valence of the metal ion, that is, varies in the range of 1 to 4 depending on the type of M. When y is an integer greater than 2, a plurality of R g4 Each other or multiple R g5 They may be the same as or different from each other.

[0360] When the resin composition of the present embodiment contains other flame retardants, the content thereof is not particularly limited, and may be, for example, 0.1 parts by mass or more relative to 100 parts by mass of component (A), or may be 50 parts by mass or less, 30 parts by mass or less, 15 parts by mass or less, 5 parts by mass or less, or 1 part by mass or less.

[0361] (Flame retardant additive)

[0362] Examples of the flame retardant aid include inorganic flame retardant aids such as antimony trioxide and zinc molybdate.

[0363] When the resin composition of the present embodiment contains a flame retardant auxiliary, its content is not particularly limited, and is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, relative to 100 parts by mass of the total resin component. If the content of the flame retardant auxiliary is within the above range, there is a tendency to obtain better chemical resistance.

[0364] (Organic Solvent)

[0365] The resin composition of the present embodiment may be a varnish-like resin composition containing an organic solvent from the viewpoint of easy handling and easy production of a prepreg described later.

[0366] Examples of the organic solvent include alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene, and mesitylene; nitrogen-containing solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; sulfur-containing solvents such as dimethyl sulfoxide; ester solvents such as γ-butyrolactone, etc. These organic solvents may be used alone or in combination of two or more.

[0367] When the resin composition of the present embodiment contains an organic solvent, its content is not particularly limited, and the solid content concentration of the resin composition of the present embodiment is preferably 30 to 90% by mass, more preferably 40 to 80% by mass, and further preferably 50 to 70% by mass. If the content of the organic solvent is within the above range, the handling property of the resin composition becomes easy, and the impregnation property of the substrate and the appearance of the manufactured prepreg become good. In addition, the adjustment of the solid content concentration of the resin in the prepreg described later becomes easy, and the manufacture of the prepreg with the desired thickness tends to become easy.

[0368] <Other ingredients>

[0369] In addition, the resin composition of the present embodiment may contain one or more of the resin materials, coupling agents, antioxidants, heat stabilizers, antistatic agents, ultraviolet light absorbers, pigments, colorants and lubricants selected from the above-mentioned components as needed within the scope of not damaging the effect of the present invention [hereinafter, sometimes referred to as "other components". ]. These components can be used alone or in combination of two or more. In addition, the resin composition of the present embodiment may not contain these components.

[0370] When the resin composition of the present embodiment contains the above-mentioned other components, their respective contents are not particularly limited, and are, for example, 0.01 parts by mass or more, 10 parts by mass or less, 5 parts by mass or less, or 1 part by mass or less, relative to 100 parts by mass of the total resin components.

[0371] In addition, the total content of the components (B), (C), (D) and (E) in the resin components contained in the resin composition of the present embodiment is not particularly limited, but is preferably 80 parts by mass or more, more preferably 90 parts by mass or more, and further preferably 95 parts by mass or more, relative to 100 parts by mass of the total resin components.

[0372] <Dielectric properties>

[0373] The dielectric constant (Dk) at 10 GHz when the resin composition of the present embodiment is made into a test piece by the method described in the examples described later is not particularly limited, and is preferably 4.5 or less, more preferably 4.3 or less, and further preferably 4.1 or less. The smaller the dielectric constant (Dk), the more preferred, and its lower limit is not particularly limited, and considering the balance with other physical properties, for example, it can be 2.5 or more, or 3.0 or more.

[0374] The dielectric loss tangent (Df) at 10 GHz when the resin composition of the present embodiment is made into a test piece by the method described in the examples described later is not particularly limited, preferably 0.0075 or less, more preferably 0.0072 or less, further preferably 0.0070 or less, further preferably 0.0068 or less, and particularly preferably 0.0066 or less. The above-mentioned dielectric loss tangent (Df) is preferably smaller, and its lower limit is not particularly limited. Considering the balance with other physical properties, it can be, for example, 0.0030 or more, 0.0040 or more, or 0.0050 or more.

[0375] It should be noted that the dielectric constant (Dk) and the dielectric loss tangent (Df) are values ​​obtained based on the cavity resonator perturbation method, and more specifically, are values ​​measured by the method described in the examples. In addition, in this specification, when only the dielectric constant is referred to, it refers to the relative dielectric constant.

[0376] The resin composition of the present embodiment can be manufactured by mixing component (A), component (B) and any component used in combination as required by a known method. At this time, each component can be dissolved or dispersed while stirring in the above-mentioned organic solvent. The conditions such as mixing order, temperature, time, etc. are not particularly limited and can be set arbitrarily.

[0377] [Prepreg]

[0378] The prepreg of the present embodiment contains the resin composition of the present embodiment and a sheet-like fiber-reinforced base material.

[0379] The prepreg can be formed using the resin composition of the present embodiment and a sheet-like fiber-reinforced substrate. For example, it can be manufactured by impregnating or applying the resin composition of the present embodiment to a sheet-like fiber-reinforced substrate, heating and drying the sheet-like fiber-reinforced substrate in a drying furnace at a temperature of 80 to 200° C. for 1 to 30 minutes to semi-cure (B-stage) the resin composition.

[0380] The solid content of the resin composition in the prepreg of the present embodiment is not particularly limited, but is preferably 30 to 90% by mass, more preferably 35 to 80% by mass, further preferably 40 to 70% by mass, and particularly preferably 45 to 60% by mass. If the solid content concentration is within the above range, there is a tendency to obtain better formability when making a laminate.

[0381] As the sheet-like fiber-reinforced substrate of the prepreg, a known sheet-like fiber-reinforced substrate used in various laminates for electrical insulating materials can be used. As the material of the sheet-like fiber-reinforced substrate, inorganic fibers such as E glass, D glass, S glass, Q glass, organic fibers such as polyimide, polyester, tetrafluoroethylene, and mixtures thereof can be cited. These sheet-like fiber-reinforced substrates have, for example, the shape of fabrics, non-woven fabrics, rovings, chopped strand mats, surface mats, and the like. In addition, the thickness of the sheet-like fiber-reinforced substrate is not particularly limited, and for example, a sheet-like fiber-reinforced substrate of 0.02 to 0.5 mm can be used. In addition, from the viewpoint of the impregnation of the resin composition, the heat resistance when the laminate is made, the moisture absorption resistance, and the processability, a sheet-like fiber-reinforced substrate surface-treated with a coupling agent or the like, a sheet-like fiber-reinforced substrate subjected to a mechanical fiber opening treatment, and the like can be used.

[0382] As a method for impregnating or coating the sheet-like fiber-reinforced base material with the resin composition, the following hot melt method or solvent method can be adopted.

[0383] The hot melt method is a method in which the resin composition does not contain an organic solvent and is (1) temporarily coated on a coating paper having good releasability from the resin composition and then laminated on a sheet-like fiber-reinforced substrate, or (2) directly coated on a sheet-like fiber-reinforced substrate using a die coater.

[0384] On the other hand, the solvent method is a method in which an organic solvent is added to a resin composition, a sheet-like fiber-reinforced substrate is immersed in the obtained resin composition, the resin composition is impregnated into the sheet-like fiber-reinforced substrate, and then the substrate is dried.

[0385] [Laminated board]

[0386] The laminated plate of the present embodiment is a laminated plate including the prepreg of the present embodiment and a metal foil.

[0387] The laminated plate of the present embodiment can be obtained by configuring a metal foil on one side or both sides of a prepreg of the present embodiment, or configuring a metal foil on one side or both sides of a structure formed by overlapping two or more prepregs of the present embodiment, and then performing heat and pressure molding. Laminated plates with metal foil are sometimes also called metal-clad laminated plates.

[0388] The metal of the metal foil is not particularly limited as long as it is a metal used for electrical insulating materials. From the viewpoint of conductivity, it can be copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, or an alloy containing one or more of these metal elements, preferably copper and aluminum, more preferably copper.

[0389] [Method for producing laminated plate]

[0390] The manufacturing method of the laminated board of the present embodiment is a manufacturing method of the laminated board having a step of heat-curing the resin composition of the present embodiment, wherein the melting point of the phosphate-based flame retardant (A) is 50 to 250°C, the above-mentioned heating and curing temperature is above the melting point of the above-mentioned (A) component, and the above-mentioned (A) component in the above-mentioned resin composition before heating and curing has a particle shape.

[0391] According to the method for producing a laminated plate of the present embodiment, the component (A) having high crystallinity is melted and diffused in the resin composition, whereby both particularly excellent dielectric properties and flame retardancy can be achieved at a high level.

[0392] The preferred range of the melting point of the phosphate ester flame retardant (A) is as described above.

[0393] The heat curing temperature may be at least the melting point of the component (A), and from the viewpoint of productivity, it may be, for example, 185° C. or higher, 200 to 300° C., or 220 to 250° C. When the heat curing temperature is within the above range, excellent dielectric properties and flame retardancy, as well as good productivity, tend to be obtained.

[0394] The pressure and time during heat curing are not particularly limited, and can be carried out, for example, within the range of 0.2 to 10 MPa and 0.1 to 5 hours. In addition, heat press molding can also be carried out by maintaining a vacuum state for 0.5 to 5 hours using vacuum pressing or the like.

[0395] [Multilayer printed wiring board]

[0396] The multilayer printed wiring board of the present embodiment contains the prepreg of the present embodiment or the laminate of the present embodiment. The multilayer printed wiring board of the present embodiment can be manufactured by using the prepreg or laminate of the present embodiment, and performing circuit forming processing based on hole opening processing, metal plating processing, etching of metal foil, etc. and multilayer bonding processing by known methods.

[0397] [Semiconductor package]

[0398] The semiconductor package of the present embodiment is obtained by mounting a semiconductor element on the multilayer printed wiring board of the present embodiment.

[0399] The semiconductor package of the present embodiment can be manufactured by, for example, mounting semiconductor elements such as semiconductor chips and memories at predetermined positions on a multilayer printed wiring board of the present embodiment by a known method and sealing the semiconductor elements with a sealing resin or the like.

[0400] The preferred embodiments of the present invention have been described above, but these are examples for explaining the present invention and are not intended to limit the scope of the present invention to these embodiments. The present invention can be implemented in various ways different from the above embodiments without departing from the gist of the present invention.

[0401] Example

[0402] Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to the following Examples.

[0403] In addition, in each example, the weight average molecular weight (Mw) was measured by the following method.

[0404] The conversion was performed by gel permeation chromatography (GPC) based on a calibration curve using standard polystyrene. The calibration curve used standard polystyrene: TSK standard POLYSTYRENE (Type; A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) [manufactured by Tosoh Corporation, trade name], and was approximated by a cubic equation. The measurement conditions of GPC are shown below.

[0405] Device:

[0406] Pump: L-6200 model [manufactured by Hitachi High-Tech Co., Ltd.]

[0407] Detector: L-3300 RI [manufactured by Hitachi High-Tech Co., Ltd.]

[0408] Column oven: L-655A-52 [manufactured by Hitachi High-Tech Co., Ltd.]

[0409] Column: guard column; TSK Guardcolumn HHR-L+ column; TSKgel G4000HHR+TSKgel G2000HHR (all manufactured by Tosoh Corporation, trade name)

[0410] Column size: 6.0×40mm (guard column), 7.8×300mm (column)

[0411] Eluent: Tetrahydrofuran

[0412] Sample concentration: 30mg / 5mL

[0413] Injection volume: 20 μL

[0414] Flow rate: 1.00mL / min

[0415] Measurement temperature: 40℃

[0416] [Production Example 1: Production of modified maleimide compound (X-1)]

[0417] In a 5-liter reaction vessel with a thermometer, a stirring device, and a moisture meter attached to a reflux condenser capable of heating and cooling, 100 parts by mass of 2,2-bis[4-(4-maleimide phenoxy) phenyl] propane, 5.6 parts by mass of a siloxane compound having amino groups at both ends (functional group equivalent 750 g / mol), 7.9 parts by mass of 3,3'-diethyl-4,4'-diaminodiphenylmethane, and 171 parts by mass of propylene glycol monomethyl ether were added, and the mixture was reacted for 2 hours while refluxing. The mixture was concentrated at reflux temperature for 3 hours to produce a modified maleimide compound (X-1) solution having a solid content concentration of 65% by mass. The weight average molecular weight (Mw) of the obtained modified maleimide compound (X-1) was about 2700.

[0418] [Examples 1 and 2, Comparative Examples 1 to 6]

[0419] The components described in Table 1 were 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 having a solid content concentration of 55 to 65% by mass.

[0420] The resin composition obtained in each example was applied to a glass fiber cloth (E glass, manufactured by Nitto Spinning Co., Ltd.) having a thickness of 0.08 mm, and then heated and dried at 150° C. for 5 minutes to produce a prepreg having a solid content of about 47% by mass from the resin composition. A low-smoothness copper foil (BF-ANP18, Rz of the M surface: 1.5 μm, manufactured by CIRCUIT FOIL) having a thickness of 18 μm was arranged above and below the prepreg in such a manner that the M surface was in contact with the prepreg, and heated and pressed under the conditions of a temperature of 230° C., a pressure of 3.0 MPa, and a time of 90 minutes to produce a double-sided copper-clad laminate (thickness: 0.10 mm).

[0421] [Evaluation method]

[0422] The double-sided copper-clad laminate obtained in each example was used to perform various evaluations according to the following methods.

[0423] (1. Dielectric properties)

[0424] The dielectric constant and dielectric loss tangent as dielectric properties are measured as follows: the outer copper foil of the double-sided copper-clad laminate is immersed in a copper etching solution (a 10% by mass solution of ammonium persulfate, manufactured by MITSUBISHI GAS CHEMICAL Co., Ltd.) to remove it, cut it into a length of 60 mm and a width of 2 mm, and use it as a test piece to measure it using the cavity resonator perturbation method. The measuring instrument uses the vector network analyzer "N5227A" manufactured by Agilent Technologies, the cavity resonator uses the "CP129" (10 GHz band resonator) manufactured by Kanto Electronics Application Development Co., Ltd., and the measuring program uses "CPMA-V2". The measurement is carried out under the conditions of a frequency of 10 GHz and a measuring temperature of 25 ° C.

[0425] (2. Flame retardancy)

[0426] The outer copper foil of the double-sided copper-clad laminate was removed by immersion in a copper etching solution (a 10 mass % solution of ammonium persulfate, manufactured by MITSUBISHI GAS CHEMICAL Co., Ltd.), and cut into a length of 127 mm and a width of 12.7 mm as a test piece. Next, according to the test method (V method) of UL94, the lower end of the test piece kept vertical was contacted with a 20 mm flame for 10 seconds twice, and the flame retardancy was evaluated according to the standard of the V method of UL94.

[0427] (3. Evaluation of copper foil peel strength)

[0428] The copper foil peel strength of the double-sided copper-clad laminate was measured in accordance with JIS C6481.

[0429] [Table 1]

[0430] Table 1

[0431]

[0432] (Except for the values ​​in parentheses, the unit of the blending composition is parts by mass. The values ​​in parentheses in the flame retardant are the content of phosphorus atoms derived from the flame retardant in the solid content of the resin composition excluding the inorganic filler (unit: mass %). In the table, "ND" means not measured.)

[0433] In addition, the abbreviations etc. of each material in Table 1 are as follows.

[0434] [(A) ingredient: flame retardant]

[0435] A-1: 4,4′-biphenol-bis(di-2,6-ditoluene phosphate) represented by the following formula (A-10), melting point: 184° C., average particle size: 1.5 μm.

[0436] [Chemical formula 33]

[0437]

[0438] A-2: Bisphenol A polyphenyl phosphate represented by the following formula (A-11).

[0439] [Chemical formula 34]

[0440]

[0441] (m represents 1.1 to 1.2.)

[0442] [Component (A'): comparative flame retardant]

[0443] A'-3: A phosphazene compound represented by the following formula (A-12).

[0444] [Chemical formula 35]

[0445]

[0446] A'-4: A phosphazene compound represented by the following formula (A-13).

[0447] [Chemical formula 36]

[0448]

[0449] A'-5: A phosphite compound represented by the following formula (A-14).

[0450] [Chemical formula 37]

[0451]

[0452] A'-6: A phosphite compound represented by the following formula (A-15).

[0453] [Chemical formula 38]

[0454]

[0455] A'-7: Terephthalidene diphenylphosphine oxide represented by the following formula (A-16).

[0456] [Chemical formula 39]

[0457]

[0458] [Component (B): polyphenylene ether derivative]

[0459] B-1: polyphenylene ether having methacryloyl groups at both terminals (weight average molecular weight (Mw) 1700).

[0460] [Component (C): Thermosetting resin]

[0461] C-1: the modified maleimide compound (X-1) prepared in Production Example 1.

[0462] [Component (D): styrene-based thermoplastic elastomer]

[0463] D-1: maleic anhydride-modified hydrogenated styrene-based thermoplastic elastomer (SEBS), acid value 10 mgCH3ONa / g, styrene content 30%, MFR 5.0 g / 10 min (MFR measurement conditions: measured at 230° and load 2.16 kg in accordance with ISO 1133).

[0464] [Component (E): curing accelerator]

[0465] ·E-1: Tri-n-butylphosphine addition product of p-benzoquinone

[0466] ·E-2:2-Undecyl imidazole

[0467] E-3: Dicyandiamide

[0468] [(F) component: inorganic filler]

[0469] Spherical fused silica: average particle size: 0.5 μm, methyl isobutyl ketone 70 mass% slurry

[0470] According to the results shown in Table 1, the laminated plates of Examples 1 and 2 prepared using the resin composition of the present embodiment have sufficient flame retardancy and copper foil peel strength, and have low dielectric loss tangent and excellent high-frequency characteristics compared to the laminated plates of Comparative Examples 1 to 6. On the other hand, the laminated plates of Comparative Examples 1 to 5 using substances other than component (A) as flame retardants, and the laminated plates of Comparative Example 6 without flame retardants have poor dielectric loss tangent or flame retardancy.

[0471] Industrial Applicability

[0472] The resin composition of the present invention has sufficient flame retardancy and exhibits excellent dielectric properties in high frequency bands above 10 GHz. Therefore, prepregs, laminates, multilayer printed wiring boards, semiconductor packages, etc. obtained using the resin composition are suitable for use in electronic components that process high frequency signals.

Claims

1. A resin composition comprising: A phosphate flame retardant (A) having an aromatic hydrocarbon group having two or more aromatic ring structures; a polyphenylene ether derivative (B) having an ethylenically unsaturated bond-containing group at both ends; and The thermosetting resin (C) is at least one selected from epoxy resins, cyanate resins and maleimide compounds, The content ratio of the polyphenylene ether derivative (B) to the thermosetting resin (C), i.e., (B) / (C), is 5 / 95 to 40 / 60 by mass ratio. The component (A) is a compound represented by the following general formula (A-1), In the formula, R a1 ~R a4 Each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom, and X a1 represents a divalent group represented by the following general formula (A-2) or a divalent condensed polycyclic aromatic hydrocarbon group containing two or more aromatic ring structures, n a1 ~n a4 Each independently represents an integer from 0 to 5, and n a5 represents an integer from 1 to 5, In the formula, R a5 and R a6 Each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom, and X a2 represents an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a thioether group, a sulfonyl group, a carbonyloxy group, a keto group or a single bond, and n a6 and n a7 Each independently represents an integer from 0 to 4, and n a8 Indicates an integer from 1 to 3.

2. The resin composition according to claim 1, wherein The aromatic hydrocarbon group containing two or more aromatic ring structures is a divalent aromatic hydrocarbon group in which two or more aromatic rings are bonded to each other via a single bond or a connecting group having 5 or less carbon atoms, or a divalent condensed polycyclic aromatic hydrocarbon group containing two or more aromatic ring structures.

3. The resin composition according to claim 1 or 2, wherein The content of phosphorus atoms derived from the component (A) is 0.2% by mass to 5% by mass in the solid content of the resin composition excluding the inorganic filler.

4. The resin composition according to claim 1 or 2, wherein The ethylenically unsaturated bond-containing group of the component (B) is a (meth)acryloyl group.

5. The resin composition according to claim 1 or 2, wherein The weight average molecular weight Mw of the component (B) is 500 to 7,000.

6. The resin composition according to claim 1, wherein The component (C) contains the maleimide compound, which 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.

7. The resin composition according to claim 6, wherein The modified maleimide compound is a compound represented by the following general formula (C-2): Where, X c1 and X c4 Each is independently a divalent organic group. 8 . The resin composition according to claim 1 , further comprising at least one selected from the group consisting of a styrene-based thermoplastic elastomer (D), a curing accelerator (E), and an inorganic filler (F). 9 . A prepreg comprising the resin composition according to claim 1 and a sheet-like fiber-reinforced base material.

10. A laminate comprising the prepreg according to claim 9 and a metal foil. 11 . A multilayer printed wiring board comprising the prepreg according to claim 9 or the laminate according to claim 10 . 12 . A semiconductor package comprising a semiconductor element mounted on the multilayer printed wiring board according to claim 11 .

13. A method for producing a laminated board, comprising the step of heat-curing the resin composition according to any one of claims 1 to 8, wherein: The melting point of the component (A) is 50°C to 250°C. The heating and curing temperature is above the melting point of the component (A). The component (A) in the resin composition before heat curing has a particle shape.

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