WO2020095422A1 - Resin composition, cured object obtained from resin composition, prepreg, laminate, resin film, multilayered printed wiring board, multilayered printed wiring board for millimeter-wave radar, and poly(phenylene ether) derivative - Google Patents

Resin composition, cured object obtained from resin composition, prepreg, laminate, resin film, multilayered printed wiring board, multilayered printed wiring board for millimeter-wave radar, and poly(phenylene ether) derivative Download PDF

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Publication number
WO2020095422A1
WO2020095422A1 PCT/JP2018/041554 JP2018041554W WO2020095422A1 WO 2020095422 A1 WO2020095422 A1 WO 2020095422A1 JP 2018041554 W JP2018041554 W JP 2018041554W WO 2020095422 A1 WO2020095422 A1 WO 2020095422A1
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WIPO (PCT)
Prior art keywords
group
resin composition
aliphatic hydrocarbon
unsaturated aliphatic
component
Prior art date
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PCT/JP2018/041554
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French (fr)
Japanese (ja)
Inventor
彩 笠原
智彦 小竹
藤本　大輔
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日立化成株式会社
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Publication date
Application filed by 日立化成株式会社 filed Critical 日立化成株式会社
Priority to JP2020556436A priority Critical patent/JP7298623B2/en
Priority to PCT/JP2018/041554 priority patent/WO2020095422A1/en
Priority to CN201880099255.4A priority patent/CN112969759A/en
Priority to TW108139894A priority patent/TWI834750B/en
Publication of WO2020095422A1 publication Critical patent/WO2020095422A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/48—Polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate

Definitions

  • the present invention relates to a resin composition, a cured product of the resin composition, a prepreg, a laminate, a resin film, a multilayer printed wiring board, a multilayer printed wiring board for millimeter wave radar, and a polyphenylene ether derivative.
  • a polyphenylene ether (PPE) resin has been used as a heat-resistant thermoplastic polymer having excellent high-frequency characteristics for a printed wiring board that requires low transmission loss.
  • PPE polyphenylene ether
  • a method of using polyphenylene ether and a thermosetting resin in combination has been proposed.
  • a resin composition containing a polyphenylene ether and an epoxy resin see, for example, Patent Document 1
  • a resin composition containing a polyphenylene ether and a cyanate resin having a low dielectric constant among thermosetting resins for example, patents Reference 2 and the like are disclosed.
  • Patent Documents 1 and 2 described above are generally insufficient in high-frequency characteristics in the GHz range, adhesiveness with conductors, low coefficient of thermal expansion, flame retardancy, and polyphenylene ether and thermosetting. In some cases, the heat resistance may decrease due to the low compatibility with the resin.
  • a resin having particularly good compatibility and having dielectric properties in a high frequency band, high adhesion with a conductor, excellent heat resistance, high glass transition temperature, low thermal expansion coefficient and high flame retardancy is composed of a polyphenylene ether derivative (A) having an N-substituted maleimide structure-containing group and a structural unit represented by the following general formula in one molecule, an epoxy resin, a cyanate resin and a maleimide compound.
  • a resin composition containing at least one thermosetting resin (B) selected from the group and a styrene-based thermoplastic elastomer (C) has been proposed (see, for example, Patent Document 3).
  • each R 1 is independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom.
  • X is an integer of 0 to 4.
  • JP 58-069046 A Japanese Patent Publication No. 61-018937 International Publication No. 2016/175326
  • Patent Document 3 Although the resin composition described in Patent Document 3 is surely excellent in the dielectric property in a high frequency band, in recent years, a fifth generation mobile communication system using radio waves in a frequency band exceeding 6 GHz ( 5G) Development of a resin composition having improved dielectric characteristics in a high frequency band, which can be used also for a millimeter wave radar in which an antenna and a radio wave in a frequency band of 30 to 300 GHz are used, has been earnestly desired, and a new resin composition has been desired. Material development is an urgent task.
  • the present invention provides a resin composition capable of exhibiting excellent dielectric properties in a high frequency band of 10 GHz or higher, a cured product of the resin composition, a prepreg, a resin film, a multilayer printed wiring board, and a millimeter. It is an object of the present invention to provide a multilayer printed wiring board for wave radar, and a polyphenylene ether derivative that makes it possible to obtain such a resin composition.
  • the present inventors have conducted extensive studies in order to solve the above problems, as a result, a polyphenylene ether derivative having a specific molecular structure, and at least one selected from the group consisting of a specific maleimide compound and its derivative. It has been found that the resin composition containing the compound exhibits excellent dielectric properties in a high frequency band of 10 GHz or higher, and has completed the present invention. That is, the present invention relates to the following [1] to [20].
  • a resin composition comprising: [2] The resin composition according to the above [1], wherein the organic group substituted by the unsaturated aliphatic hydrocarbon group contained in the component (A) has a structure represented by the following general formula (a-1).
  • R a1 is an unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms.
  • M1 is 1 or 2
  • n1 is 0 or 1. * represents another structure.
  • the unsaturated aliphatic hydrocarbon group is a vinyl group, an isopropenyl group, an allyl group, a 1-methylallyl group or a 3-butenyl group, and the above [1] to [5] The resin composition according to any one of 1.
  • X B1 and X B2 are each independently an organic group.
  • a multilayer printed wiring board containing at least one selected from the group consisting of the prepreg described in [10] above, the laminated board described in [11] above, and the resin film described in [12] above. .. [14] A millimeter wave radar including at least one selected from the group consisting of the prepreg described in [10] above, the laminated plate described in [11] above and the resin film described in [12] above. Multilayer printed wiring board. [15] A polyphenylene ether derivative having an organic group substituted with an unsaturated aliphatic hydrocarbon group.
  • R a2 and R a3 are each independently an unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms. * Represents a bonding position to another structure.
  • [18] The polyphenylene ether derivative according to any one of the above [15] to [17], wherein the total number of the unsaturated aliphatic hydrocarbon groups is 2 or more.
  • [19] The polyphenylene ether derivative according to any one of the above [15] to [18], wherein the total number of the unsaturated aliphatic hydrocarbon groups is 4 or more.
  • a resin composition capable of exhibiting excellent dielectric properties (low dielectric constant and low dielectric loss tangent) in a high frequency band of 10 GHz or higher, a cured product of the resin composition, a prepreg, a resin film, and a multilayer print. It is possible to provide a wiring board, a multilayer printed wiring board for millimeter-wave radar, and a polyphenylene ether derivative that makes it possible to obtain such a resin composition.
  • the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.
  • the lower limit value and the upper limit value of the numerical range are arbitrarily combined with the lower limit value and the upper limit value of the other numerical range.
  • each component and material exemplified in the present specification may be used alone or in combination of two or more unless otherwise specified.
  • the content of each component in the composition is the total amount of the plurality of substances present in the composition, unless a plurality of substances corresponding to each component are present in the composition.
  • Means The present invention also includes an embodiment in which the items described in this specification are arbitrarily combined.
  • One aspect of the present invention is (A) Polyphenylene ether derivative having an organic group substituted with an unsaturated aliphatic hydrocarbon group [hereinafter, may be simply referred to as polyphenylene ether derivative (A) or component (A)], and (B) N-substituted At least one kind selected from the group consisting of a maleimide compound having at least two maleimide groups and a derivative thereof [hereinafter, sometimes simply referred to as maleimide compound (B) or (B) component], It is a resin composition containing.
  • each component will be described in detail in order.
  • the polyphenylene ether derivative (A) has an organic group substituted with an unsaturated aliphatic hydrocarbon group, and preferably has an organic group substituted with an unsaturated aliphatic hydrocarbon group at least at one end.
  • the present invention also provides the polyphenylene ether derivative (A) itself.
  • the organic group substituted with the unsaturated aliphatic hydrocarbon group may be present at one end of the component (A), may be present at both ends of the component (A), or may be present in the central skeleton.
  • a polyphenylene ether derivative having an organic group substituted with an unsaturated aliphatic hydrocarbon group at one end a polyphenylene ether derivative having an organic group substituted with an unsaturated aliphatic hydrocarbon group at both ends, and It may be a mixture of two or more kinds selected from the group consisting of polyphenylene ether derivatives having an organic group substituted with an unsaturated aliphatic hydrocarbon group in the central skeleton.
  • the component (A) preferably contains a polyphenylene ether derivative having an organic group substituted with an unsaturated aliphatic hydrocarbon group at one terminal, and an organic group substituted with an unsaturated aliphatic hydrocarbon group at one terminal More preferably, it is the polyphenylene ether derivative itself.
  • the component (A) contains a polyphenylene ether derivative having an organic group substituted with an unsaturated aliphatic hydrocarbon group at one end, in the component (A), an unsaturated aliphatic hydrocarbon group was substituted at one end
  • the content of the polyphenylene ether derivative having an organic group may be 30% by mass or more, 45% by mass or more, 55% by mass or more, and 70% by mass or more. It may be 90% by mass or more, or may be substantially 100% by mass.
  • Examples of the “unsaturated aliphatic hydrocarbon group” in the “organic group substituted with an unsaturated aliphatic hydrocarbon group” included in the component (A) include, for example, vinyl group, isopropenyl group, allyl group and 1-methylallyl group. , 3-butenyl group and the like. Among these, an unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms is preferable, and an unsaturated aliphatic hydrocarbon group having 2 to 5 carbon atoms is more preferable, from the viewpoint of dielectric properties in a high frequency band of 10 GHz band or higher. , And allyl groups are more preferred.
  • the unsaturated aliphatic hydrocarbon group A group that cannot be said to be a hydrogen group is not included in the "unsaturated aliphatic hydrocarbon group" in the above "organic group substituted with an unsaturated aliphatic hydrocarbon group”.
  • the total number of unsaturated aliphatic hydrocarbon groups contained in the component (A) is preferably 2 or more, more preferably 4 or more, from the viewpoint of dielectric properties in a high frequency band of 10 GHz band or more, and the upper limit value.
  • the total number of unsaturated aliphatic hydrocarbon groups at one end of the component (A) is preferably 2 or more, more preferably 4 from the viewpoint of dielectric properties in a high frequency band of 10 GHz band or higher.
  • the upper limit value is not particularly limited and may be 8 or less, or 6 or less.
  • the total number of unsaturated aliphatic hydrocarbon groups contained in the component (A) and the total number of unsaturated aliphatic hydrocarbon groups contained in one end of the component (A) are four. .
  • the “unsaturated aliphatic hydrocarbon group-substituted organic group” preferably has a structure represented by the following general formula (a-1) from the viewpoint of dielectric properties in a high frequency band of 10 GHz or higher.
  • R a1 is an unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms.
  • M1 is 1 or 2
  • n1 is 0 or 1.
  • * represents another structure. The binding position to is shown.
  • Examples of the unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms represented by R a1 in the above general formula (a-1) include a vinyl group, an isopropenyl group, an allyl group, a 1-methylallyl group, and 3-butenyl. Groups and the like. Among these, an unsaturated aliphatic hydrocarbon group having 2 to 5 carbon atoms is preferable, and an allyl group is more preferable, from the viewpoint of dielectric characteristics in a high frequency band of 10 GHz or higher.
  • m1 may be 1 or 2, but is preferably 1.
  • n1 may be 0 or 1.
  • the “organic group substituted with an unsaturated aliphatic hydrocarbon group” has a structure represented by the above general formula (a-1), at least the “organic group substituted with an unsaturated aliphatic hydrocarbon group”
  • the structure represented by the general formula (a-1) may be included in part.
  • the "unsaturated aliphatic hydrocarbon group-substituted organic group” is represented by the following general formula (a-2) from the viewpoint of dielectric properties and compatibility in a high frequency band of 10 GHz or higher.
  • An embodiment having a structure is also preferable.
  • R a2 and R a3 are each independently an unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms. * Represents a bonding position to another structure.
  • Examples of the unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms represented by R a2 and R a3 in the general formula (a-2) include the same ones as R a1 in the general formula (a-1). , The same is preferable.
  • the “organic group substituted with an unsaturated aliphatic hydrocarbon group” has a structure represented by the above general formula (a-2), at least the “organic group substituted with an unsaturated aliphatic hydrocarbon group”
  • the structure represented by the general formula (a-2) may be included in part.
  • the “organic group substituted with an unsaturated aliphatic hydrocarbon group” is one of the following general formulas (a-3) to (a-5) from the viewpoint of dielectric properties in a high frequency band of 10 GHz or higher.
  • the structure represented by the following general formula (a-5) is more preferable from the viewpoint of dielectric properties and compatibility in a high frequency band of 10 GHz or higher.
  • R a4 is an unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms. * Represents a bonding position to another structure.
  • R a5 and R a6 are each independently an unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms.
  • X a1 is an aliphatic hydrocarbon group having 1 to 6 carbon atoms. It is a group. * Indicates a bonding position to another structure.
  • R a7 to R a10 are each independently an unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms.
  • X a2 is an organic group. * Is another structure. The binding position to is shown.
  • Examples of the unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms represented by R a4 to R a10 in the general formulas (a-3) to (a-5) include R a1 in the general formula (a-1).
  • Examples of the aliphatic hydrocarbon group having 1 to 6 carbon atoms represented by X a1 in the general formula (a-4) include alkylene groups having 1 to 6 carbon atoms such as methylene group, ethylene group and trimethylene group; Examples thereof include an alkylidene group having 2 to 6 carbon atoms such as a lidene group.
  • the organic group represented by X a2 in the general formula (a-5) is an aliphatic hydrocarbon group which may partially contain a hetero atom, or an aliphatic hydrocarbon group which may partially contain a hetero atom. Examples thereof include a cyclic hydrocarbon group, an aromatic hydrocarbon group which may partially contain a hetero atom, and a group composed of any combination thereof. Examples of the hetero atom include an oxygen atom, a nitrogen atom and a sulfur atom.
  • the organic group represented by X a2 is preferably a group containing no hetero atom from the viewpoint of dielectric properties in a high frequency band of 10 GHz or higher, and an aliphatic hydrocarbon group containing no hetero atom,
  • An alicyclic hydrocarbon group containing no heteroatoms is more preferable, and it is a group consisting of a combination of an aliphatic hydrocarbon group containing no heteroatoms and an alicyclic hydrocarbon group containing no heteroatoms. It is more preferable that there is.
  • more preferable embodiments are the following formulas from the viewpoint of the dielectric properties in the high frequency band of 10 GHz band or higher. a-3 ′), (a-4 ′) or (a-5 ′).
  • the structure represented by the following formula (a-4 ′) or (a-5 ′) is more preferable from the viewpoint of dielectric properties and compatibility in a high frequency band of 10 GHz or higher, and the following formula (a The structure represented by -5 ') is more preferable.
  • X a2 is the same as X a2 in the above general formula (a-5). * Represents a bonding position to another structure.
  • component (A) is a polyphenylene ether derivative
  • component (A) is a polyphenylene ether derivative
  • R a11 is each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom.
  • P1 is an integer of 0 to 4.
  • R a11 in the general formula (I) is each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom.
  • the aliphatic hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group and the like.
  • the aliphatic hydrocarbon group an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferable, and a methyl group is more preferable.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • R a11 is preferably an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
  • p1 is an integer of 0 to 4, and may be an integer of 0 to 2 or 2.
  • R a11 may be substituted at the ortho position on the benzene ring (however, based on the substitution position of the oxygen atom).
  • the plurality of R a11 's may be the same or different.
  • the structural unit represented by the general formula (I) may be specifically a structural unit represented by the following general formula (I ′).
  • the polyphenylene ether derivative (A) may contain a polyphenylene ether derivative represented by any of the following general formulas (Ai) to (A-iii), and in particular, the following general formula (A-ii) or It preferably contains a polyphenylene ether derivative represented by (A-iii), and more preferably contains a polyphenylene ether derivative represented by the following general formula (A-iii).
  • X a2 is the formula (a-5)
  • X a2 to be the same .q1 ⁇ q3 in are each independently an integer of 1 to 200.
  • q1 to q3 are each independently an integer of 1 to 200, and the phase of the resin composition and the viewpoint of dielectric properties in a high frequency band of 10 GHz band or higher. From the viewpoint of compatibility, it is preferably an integer of 1 to 150, more preferably an integer of 1 to 120, still more preferably an integer of 1 to 100.
  • the lower limit value of the numerical range of q1 to q3 may be 10 or more, 20 or more, or 25 or more.
  • a mixture of polyphenylene ether derivatives having different values of q1 to q3 may be used, and usually tends to be a mixture.
  • the number average molecular weight of the polyphenylene ether derivative (A) is preferably 1,000 to 25,000.
  • the number average molecular weight of the polyphenylene ether derivative (A) is 1,000 or more, the dielectric property in the high frequency band of 10 GHz band or more tends to be further improved.
  • the number average molecular weight of the polyphenylene ether derivative (A) is 25,000 or less, the compatibility of the resin composition becomes good, and it tends to be difficult to separate even if left for a long time.
  • the number average molecular weight of the polyphenylene ether derivative (A) is more preferably 2,000 to 20,000, further preferably 2,500 to 15,000, still more preferably 3,000 to 10,000. , Particularly preferably 3,000 to 7,500, most preferably 3,000 to 6,000.
  • the number average molecular weight is a value converted from a calibration curve using standard polystyrene by gel permeation chromatography (GPC), and more specifically, measurement of the number average molecular weight described in Examples. It is the value obtained by the method.
  • a raw material polyphenylene ether produced by polymerization is mixed with an unsaturated aliphatic hydrocarbon group-containing phenol compound (1), and a reaction catalyst described later is added if necessary.
  • a reaction catalyst described later is added if necessary.
  • the oxy radical of the unsaturated aliphatic hydrocarbon group-containing phenol compound (1) attacks the carbon atom to which the oxygen atom in the raw material polyphenylene ether is bonded, and the OC bond is broken there, resulting in a low molecular weight. It is a reaction that changes.
  • the attacked oxy radical of the unsaturated aliphatic hydrocarbon group-containing phenol compound (1) is bonded to the carbon atom whose bond has been broken, and is incorporated into the structure of the polyphenylene ether.
  • a known method can be used and applied as the redistribution reaction.
  • the molecular weight of the polyphenylene ether derivative (A) can be controlled by the amount of the unsaturated aliphatic hydrocarbon group-containing phenol compound (1) used, and the amount of the unsaturated aliphatic hydrocarbon group-containing phenol compound (1) used is The higher the amount, the lower the molecular weight of the polyphenylene ether derivative (A). That is, the amount of the unsaturated aliphatic hydrocarbon group-containing phenol compound (1) used may be appropriately adjusted so that the number average molecular weight of the finally produced polyphenylene ether derivative (A) falls within a suitable range.
  • the amount of the unsaturated aliphatic hydrocarbon group-containing phenol compound (1) to be used is not particularly limited, but for example, the amount of the raw material polyphenylene ether to be reacted with the unsaturated aliphatic hydrocarbon group-containing phenol compound (1) When the number average molecular weight is 10,000 to 30,000, the unsaturated aliphatic hydrocarbon group-containing phenol compound (1) is used in an amount of 1 to 10 mol per 1 mol of the raw material polyphenylene ether.
  • the polyphenylene ether derivative (A) having a number average molecular weight within the above-mentioned preferable range can be obtained.
  • the organic solvent used in the production process of the polyphenylene ether derivative (A) is not particularly limited, but examples thereof include alcohols such as methanol, ethanol, butanol, butyl cellosolve, ethylene glycol monomethyl ether, propylene glycol monomethyl ether; acetone, methyl ethyl ketone, methyl.
  • Ketones such as isobutyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and mesitylene; esters such as methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate, ethyl acetate; N, N-dimethylformamide, N, N-dimethyl Examples thereof include nitrogen-containing compounds such as acetamide and N-methyl-2-pyrrolidone. These may be used alone or in combination of two or more. Among these, toluene, xylene, and mesitylene may be selected from the viewpoint of solubility, and it is preferable to select toluene.
  • a reaction catalyst can be used as necessary as described above.
  • the reaction catalyst include, for example, an organic peroxide such as t-butylperoxyisopropyl monocarbonate and a carboxylic acid such as manganese naphthenate from the viewpoint of obtaining a polyphenylene ether derivative (A) having a stable and reproducible number average molecular weight. It is preferable to use together with a metal salt.
  • the amount of the reaction catalyst used is not particularly limited.
  • organic The peroxide may be 0.5 to 5 parts by mass and the carboxylic acid metal salt may be 0.05 to 0.5 parts by mass.
  • the unsaturated aliphatic hydrocarbon group-containing phenol compound (1), the raw material polyphenylene ether having the number average molecular weight of 10,000 to 30,000, an organic solvent and, if necessary, a reaction catalyst are charged in a predetermined amount in a reactor, and heated and kept warm.
  • the polyphenylene ether derivative (A) is obtained by reacting with stirring.
  • the reaction temperature and reaction time in this step can be appropriately adjusted according to known reaction conditions during redistribution reaction. From the viewpoint of workability and suppression of gelation, and from the viewpoint of obtaining the component (A) having the desired number average molecular weight, the reaction may be carried out, for example, at a reaction temperature of 70 to 110 ° C. and a reaction time of 1 to 8 hours.
  • reaction concentration The solid content concentration (hereinafter referred to as reaction concentration) during the reaction in the production process of the polyphenylene ether derivative (A) is not particularly limited, but may be, for example, 10 to 60% by mass, 25 It may be up to 55 mass%.
  • reaction concentration 10% by mass or more, the reaction rate does not become too slow, and the production cost tends to be more advantageous.
  • reaction temperature is 60% by mass or less, better solubility tends to be obtained, and further, the solution viscosity is low, stirring efficiency is good, and gelation tends to be difficult.
  • the solution of the polyphenylene ether derivative (A) produced as described above may be concentrated as necessary to remove a part of the organic solvent as described below, or may be diluted by adding an organic solvent. May be.
  • the resin composition of the present invention tends to have better dielectric properties in a high frequency band of 10 GHz or higher than a resin composition containing the raw material polyphenylene ether instead of the component (A).
  • the maleimide compound (B) is at least one selected from the group consisting of maleimide compounds having at least two N-substituted maleimide groups and derivatives thereof.
  • the maleimide compound (B) does not include the polyphenylene ether derivative (A).
  • the maleimide compound (B) does not contain the structural unit represented by the general formula (I), in other words, does not contain the polyphenylene ether skeleton.
  • Examples of the “derivative thereof” include addition reaction products of the maleimide compound having at least two N-substituted maleimide groups and an amine compound such as a diamine compound (b2) described later.
  • the maleimide compound (B) has at least two N-substituted maleimide groups from the viewpoints of solubility in an organic solvent, compatibility, adhesion with a conductor, and dielectric properties in a high frequency band of 10 GHz or higher.
  • a maleimide compound derivative is preferable, and a maleimide compound (b1) having at least two N-substituted maleimide groups [hereinafter, may be simply referred to as maleimide compound (b1) or (b1) component).
  • the structural unit derived from the component (b1) and the structural unit derived from the component (b2) may be of one type or a combination of two or more types.
  • component (b1) are not particularly limited as long as they are maleimide compounds having two or more N-substituted maleimide groups, and examples thereof include bis (4-maleimidophenyl) methane, polyphenylmethanemaleimide, bis (4- Maleimidophenyl) ether, bis (4-maleimidophenyl) sulfone, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide, 4-methyl-1,3-phenylenebismaleimide, m -Aromatic maleimide compounds such as phenylene bismaleimide, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane; 1,6-bismaleimide- (2,2,4-trimethyl) hexane, pyrrolilonic acid binder
  • Examples include aliphatic maleimide compounds such as long-chain alkyl bismaleimide.
  • aromatic maleimide compounds are preferable from the viewpoint of adhesiveness to conductors and mechanical properties, and 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, 3,3′-dimethyl-5, More preferred is 5'-diethyl-4,4'-diphenylmethane bismaleimide.
  • Examples of the structural unit derived from the component (b1) include at least one selected from the group consisting of a group represented by the following general formula (B-1) and a group represented by the following general formula (B-2). Be done.
  • X B1 represents an organic group
  • * represents a bonding position to another structure.
  • X B1 in the general formulas (B-1) and (B-2) is an organic group and corresponds to the residue of the component (b1).
  • the residue of the component (b1) refers to the structure of the part excluding the functional group used for the bond, that is, the maleimide group, from the component (b1).
  • Examples of the organic group represented by X B1 include groups represented by general formulas (II), (III), (IV) or (V) shown below.
  • each of R b1 is independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom.
  • P is an integer of 0 to 4.
  • Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R b1 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • p is an integer of 0 to 4, and from the viewpoint of easy availability, it may be an integer of 0 to 2, 0 or 1, or 0. When p is an integer of 2 or more, a plurality of R b1 's may be the same or different.
  • R b2 and R b3 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom.
  • W 2 is an alkylene group having 1 to 5 carbon atoms, an alkylidene having 2 to 5 carbon atoms.
  • the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R b2 and R b3 the same ones as in the case of R b1 can be mentioned.
  • the aliphatic hydrocarbon group may be an aliphatic hydrocarbon group having 1 to 3 carbon atoms, a methyl group, an ethyl group, or an ethyl group.
  • Examples of the alkylene group having 1 to 5 carbon atoms represented by W 2 include methylene group, 1,2-dimethylene group, 1,3-trimethylene group, 1,4-tetramethylene group, and 1,5-pentamethylene group. Is mentioned.
  • the alkylene group is an alkylene group having 1 to 3 carbon atoms from the viewpoints of high-frequency characteristics (low dielectric constant, low dielectric loss tangent), adhesion with conductors, heat resistance, glass transition temperature, thermal expansion coefficient and flame retardancy. Or may be a methylene group.
  • Examples of the alkylidene group having 2 to 5 carbon atoms represented by W 2 include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group and an isopentylidene group.
  • W 2 may be an alkylene group having 1 to 5 carbon atoms or an alkylidene group having 2 to 5 carbon atoms.
  • q and r are each independently an integer of 0 to 4, and from the viewpoint of easy availability, each may be an integer of 0 to 2 or 0 or 2.
  • q or r is an integer of 2 or more, a plurality of R b2 s or a plurality of R b3 s may be the same or different.
  • the groups represented by general formula (III-1) represented by W 2 are as follows.
  • R b4 and R b5 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom.
  • W 3 is an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, an ether group, It is a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group or a single bond.
  • S and t are each independently an integer of 0 to 4.
  • the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R b4 and R b5 are the same as those described for R b1 .
  • Examples of the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by W 3 include the same ones as the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by W 2. Be done.
  • an alkylidene group having 2 to 5 carbon atoms may be selected from the above options.
  • s and t are integers of 0 to 4, and from the viewpoint of easy availability, each may be an integer of 0 to 2, 0 or 1, or 0.
  • the plurality of R b4 s or the plurality of R b5 s may be the same or different.
  • n is an integer of 0 to 10.
  • n may be an integer of 0 to 5 or an integer of 0 to 3.
  • R b6 and R b7 are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
  • U is an integer of 1 to 8.
  • the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R b6 and R b7 is explained in the same manner as in the case of R b1 .
  • u is an integer of 1 to 8, may be an integer of 1 to 3, and may be 1.
  • X B1 in the general formulas (B-1) and (B-2) is, for example, adhesion to a conductor, heat resistance, glass transition temperature, coefficient of thermal expansion, flame retardancy, and high frequency band of 10 GHz or higher.
  • a group represented by any of the following formulas (X B1 -1) to (X B1 -3) is preferable, and a group represented by the following formula (X B1 -3) More preferably.
  • both X B1 is a group represented by the following formula (X B1 -1) and a group represented by the following formula (X B1 -3).
  • X B1 may have both a group represented by the group and the following formula represented by the following formula (X B1 -2) (X B1 -3) .. (The wavy line indicates the bonding position with the nitrogen atom in the maleimide group.)
  • the total content of the structural units derived from the component (b1) in the maleimide compound (B) is preferably 5 to 95% by mass, more preferably 30 to 93% by mass, further preferably 60 to 90% by mass, and 75 to 90% by mass. Mass% is particularly preferred.
  • the content of the structural unit derived from the component (b1) is within the above range, the dielectric property in the high frequency band of 10 GHz band or higher tends to be better, and the good film handling property tends to be obtained.
  • the component (b2) is not particularly limited as long as it is a compound having two amino groups.
  • Examples of the component (b2) 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'
  • 4,4′-diaminodiphenylmethane and 4,4′-diamino are preferable as they are excellent in solubility in an organic solvent, reactivity with the component (b1), and heat resistance.
  • the component (b2) is 3,3′-dimethyl-5,5′-diethyl-4,4′-diaminodiphenylmethane from the viewpoint of excellent dielectric properties and low water absorption in the high frequency band of 10 GHz or higher.
  • the component (b2) is preferably 2,2-bis [4- (4-aminophenoxy) phenyl] propane, from the viewpoint of excellent adhesiveness with a conductor, mechanical properties such as elongation and breaking strength.
  • the component (b2) is 4,4 ′-[1,3-phenylenebis (1-methylethylidene)] bisaniline, 4,4 ′-[1,4-phenylenebis (1-methylethylidene)] bisaniline. Is preferred.
  • the structural unit derived from the component (b2) is, for example, at least one selected from the group consisting of a group represented by the following general formula (B-3) and a group represented by the following general formula (B-4). Is mentioned.
  • X B2 in the general formulas (B-3) and (B-4) is an organic group and corresponds to the residue of the component (b2).
  • the residue of the component (b2) refers to the structure of the portion excluding the functional group provided for binding, that is, the amino group, from the component (b2).
  • X B2 in the general formula (B-3) and the general formula (B-4) is preferably a group represented by the following general formula (VI).
  • R b11 and R b12 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group or a halogen atom.
  • W 4 is 1 to 5 carbon atoms.
  • R b13 and R b14 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom.
  • W 5 is an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, or m-phenylene. It is a diene isopropylidene group, a p-phenylene diisopropylidene group, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group or a single bond, and s'and t'are each independently an integer of 0 to 4. .
  • R b15 is an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom.
  • W 6 and W 7 are each independently an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, an ether group, It is a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group or a single bond, and w is an integer of 0 to 4.
  • the general formula (VI), (VI-1 ) or (VI-2) R b11, R b12, R b13, R b14 and aliphatic hydrocarbon group, or a halogen atom having 1 to 5 carbon atoms represented by R b15 in Are the same as R b1 in the general formula (II).
  • the aliphatic hydrocarbon group may be an aliphatic hydrocarbon group having 1 to 3 carbon atoms, or may be a methyl group or an ethyl group.
  • the total content of the structural units derived from the component (b2) in the maleimide compound (B) is preferably 5 to 95% by mass, more preferably 7 to 70% by mass, further preferably 10 to 40% by mass. Mass% is particularly preferred.
  • the content of the structural unit derived from the component (b2) is within the above range, the dielectric properties in the high frequency band of 10 GHz or higher are excellent, and more favorable heat resistance, flame retardancy, and glass transition temperature tend to be obtained. It is in.
  • the content ratio of the structural unit derived from the component (b1) and the structural unit derived from the component (b2) in the maleimide compound (B) is calculated from the —NH 2 group derived from the component (b2) in the maleimide compound (B).
  • the equivalent ratio (Ta2 / Ta1) between the total equivalent (Ta2) of the group (including —NH 2 ) and the total equivalent (Ta1) of the group (including the maleimide group) derived from the maleimide group derived from the component (b1) is , 0.05 to 10 is preferable, and 1.0 to 5 is more preferable.
  • the equivalent ratio (Ta2 / Ta1) is in the above range, the dielectric properties in the high frequency band of 10 GHz or higher are excellent, and more favorable heat resistance, flame retardancy and glass transition temperature tend to be obtained.
  • the maleimide compound (B) is represented by the following general formula (B-, from the viewpoint of dielectric properties in a high frequency band of 10 GHz or higher, the solubility in an organic solvent, the high adhesion with a conductor, the moldability of a film, etc. It is preferable to include a polyamino bismaleimide compound represented by 5).
  • the polyamino bismaleimide compound (B1) having the structural unit derived from the maleimide compound (b1) and the structural unit derived from the diamine compound (b2) is, for example, a component (b1) and a component (b2) in an organic solvent. It can be produced by reacting.
  • a reaction catalyst may be used, if necessary.
  • reaction catalyst examples include, but are not limited to, acidic catalysts such as p-toluenesulfonic acid; amines such as triethylamine, pyridine and tributylamine; imidazoles such as methylimidazole and phenylimidazole; triphenylphosphine and the like.
  • acidic catalysts such as p-toluenesulfonic acid
  • amines such as triethylamine, pyridine and tributylamine
  • imidazoles such as methylimidazole and phenylimidazole
  • triphenylphosphine triphenylphosphine and the like.
  • phosphorus-based catalysts examples include These may be used alone or in combination of two or more.
  • the amount of the reaction catalyst blended is not particularly limited, but may be, for example, 0.01 to 5 parts by mass based on 100 parts by mass of the total amount of the components (b1) and (b2).
  • the polyamino bismaleimide compound is obtained by charging a predetermined amount of the component (b1), the component (b2) and, if necessary, other components into a synthesis kettle and subjecting the component (b1) and the component (b2) to a Michael addition reaction.
  • the reaction conditions in this step are not particularly limited, but the reaction temperature is preferably 50 to 160 ° C., and the reaction time is preferably 1 to 10 hours from the viewpoints of workability such as reaction rate and suppression of gelation. ..
  • the solid content concentration and solution viscosity of the reaction raw material can be adjusted by adding or concentrating the organic solvent.
  • the solid content concentration of the reaction raw material is not particularly limited, but for example, preferably 10 to 90% by mass, more preferably 20 to 80% by mass.
  • the solid content concentration of the reaction raw material is 10% by mass or more, the reaction rate does not become too slow, and the production cost tends to be advantageous. Further, when the solid content concentration of the reaction raw material is 90% by mass or less, better solubility is obtained, stirring efficiency is improved, and gelation tends to be difficult.
  • the number average molecular weight of the polyamino bismaleimide compound (B1) thus obtained is not particularly limited, but is preferably 400 to 10,000, more preferably 500 to 5,000, further preferably 500 to 2,000, and 500 to 1 , 300 is particularly preferred.
  • the number average molecular weight of the polyamino bismaleimide compound (B1) can be determined by the method described in Examples.
  • the content of the component (A) is not particularly limited, but from the viewpoint of dielectric properties in a high frequency band of 10 GHz or higher, the total amount of the resin components in the resin composition is 100 parts by mass. On the other hand, it is preferably 1 part by mass or more, more preferably 1 to 20 parts by mass, further preferably 3 to 10 parts by mass, and particularly preferably 3 to 7 parts by mass.
  • the “resin component” refers to the above-mentioned components (A) and (B), and optionally the components (C) and (G).
  • the “resin component” refers to the components (A) and (B), and the resin composition includes the components (C) and (G).
  • the “resin component” includes the components (A) and (B) as well as those components further contained.
  • the content of the component (B) is not particularly limited, but from the viewpoint of dielectric properties and moldability in a high frequency band of 10 GHz or higher, it is 10 to 10 parts by mass based on 100 parts by mass of the resin components in the resin composition.
  • the amount is preferably 90 parts by mass, more preferably 20 to 80 parts by mass, further preferably 30 to 70 parts by mass, and particularly preferably 35 to 60 parts by mass.
  • the content ratio [(A) / (B)] of the component (A) and the component (B) is not particularly limited, but may be 1/99 to 80/20 in mass ratio, and may be 3/97. To 75/25, 5/95 to 70/30, 5/95 to 50/50, 5/95 to 20/80, 5 It may be / 95 to 15/85.
  • the content ratio of the component (A) to the total amount of the component (A) and the component (B) is 1% by mass or more, excellent dielectric properties tend to be obtained in a high frequency band of 10 GHz band or higher. Further, if it is 80% by mass or less, heat resistance, moldability and workability tend to be excellent.
  • the resin composition of one aspect of the present invention may further contain other components.
  • a styrene-based thermoplastic elastomer (C) [hereinafter, may be referred to as a component (C). ]
  • Inorganic filler (D) [Hereinafter, it may be called a (D) component. ]
  • a hardening accelerator (E) [Hereinafter, it may be called a (E) component. ]
  • a flame retardant (F) [Hereinafter, it may be called a (F) component. ]
  • thermoplastic elastomer (C) By incorporating the styrene-based thermoplastic elastomer (C) in the resin composition of the present invention, dielectric properties in a high frequency band of 10 GHz or higher, moldability, adhesiveness with a conductor, solder heat resistance, glass transition temperature, heat The expansion coefficient and flame retardancy are good, and the balance between them tends to be good.
  • R c1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
  • R c2 is an alkyl group having 1 to 5 carbon atoms
  • k is an integer of 0 to 5.
  • the alkyl group having 1 to 5 carbon atoms represented by R c1 and R c2 include a methyl group, an ethyl group, an n-propyl group, and the like, which may be an alkyl group having 1 to 3 carbon atoms. It may be a group.
  • R c1 may be a hydrogen atom.
  • k may be an integer of 0 to 2, may be 0 or 1, and may be 0.
  • the structural unit other than the structural unit derived from the styrene compound included in the styrene-based thermoplastic elastomer (C) a structural unit derived from butadiene, a structural unit derived from isoprene, a structural unit derived from maleic acid, a structural unit derived from maleic anhydride Etc.
  • the styrene-based thermoplastic elastomer (C) one type may be used alone, or two or more types may be used in combination.
  • the butadiene-derived structural unit and the isoprene-derived structural unit may be hydrogenated. When hydrogenated, the structural unit derived from butadiene is a structural unit in which ethylene units and butylene units are mixed, and the structural unit derived from isoprene is a structural unit in which ethylene units and propylene units are mixed.
  • styrene-based thermoplastic elastomer (C) a styrene-butadiene-styrene block copolymer is used in view of dielectric properties in a high frequency band of 10 GHz band or higher, adhesiveness with a conductor, heat resistance, glass transition temperature and coefficient of thermal expansion. At least one selected from the group consisting of a combined hydrogenated product (SEBS, SBBS), a styrene-isoprene-styrene block copolymer hydrogenated product (SEPS), and a styrene-maleic anhydride copolymer (SMA).
  • SEBS combined hydrogenated product
  • SBBS a styrene-isoprene-styrene block copolymer hydrogenated product
  • SMA styrene-maleic anhydride copolymer
  • it is at least one selected from the group consisting of hydrogenated products of styrene-butadiene-styrene block copolymer (SEBS) and hydrogenated products of styrene-isoprene-styrene block copolymer (SEPS). Is more preferable.
  • SEBS styrene-butadiene-styrene block copolymer
  • SEPS hydrogenated products of styrene-isoprene-styrene block copolymer
  • SEBS having a carbon-carbon double bond hydrogenation rate of usually 90% or more (or 95% or more) may be used, SBBS with partially hydrogenated carbon-carbon double bonds at the 1,2-bonding sites in the butadiene block (see left below) (hydrogenation ratio of the total carbon-carbon double bonds is about 60-85%) )
  • SBBS may have cross-linking performance, and in that case, it may be contained in the cross-linking agent (G) described below, but in the present invention, even if it has cross-linking performance, the styrene-based thermoplastic elastomer is Is classified as a component (C).
  • the component (C) may be one that does not have cross-linking performance, that is, may be a hydrogenated styrene thermoplastic elastomer, and its hydrogen conversion rate is preferably 70% or more, more preferably Is 80% or more, more preferably 90% or more, particularly preferably 95% or more, and most preferably 99% or more.
  • the content of the structural unit derived from styrene (hereinafter, may be abbreviated as styrene content) is dielectric properties in a high frequency band of 10 GHz band or higher, adhesiveness with a conductor, heat resistance, glass transition. From the viewpoint of temperature and coefficient of thermal expansion, it may be 5 to 80% by mass, 5 to 70% by mass, 10 to 70% by mass, or 10 to 50% by mass. Good.
  • the melt flow rate (MFR) of SEBS is not particularly limited, but may be 0.1 to 20 g / 10 min under the measurement conditions of 230 ° C. and a load of 2.16 kgf (21.2 N), and 0.5 to It may be 15 g / 10 min.
  • SEBS examples of commercially available products of SEBS include Tuftec (registered trademark) H series and M series manufactured by Asahi Kasei Chemicals Corporation, Septon (registered trademark) series manufactured by Kuraray Co., Ltd., and Kraton (registered trademark) manufactured by Kraton Polymer Japan Co., Ltd. G polymer series etc. are mentioned.
  • the styrene content may be 40 to 80 mass% from the viewpoint of dielectric properties in a high frequency band of 10 GHz band or higher, adhesiveness with a conductor, heat resistance, glass transition temperature and coefficient of thermal expansion. , 50 to 75% by mass, or 55 to 75% by mass.
  • the melt flow rate (MFR) of SBBS is not particularly limited, but may be 0.1 to 10 g / 10 min under the measurement conditions of 190 ° C. and a load of 2.16 kgf (21.2 N), and 0.5 to It may be 10 g / 10 min or 1 to 6 g / 10 min.
  • Examples of commercial products of SBBS include Tuftec (registered trademark) P series manufactured by Asahi Kasei Chemicals Corporation.
  • the hydrogenation rate of the hydrogenated product (SEPS) of the styrene-isoprene-styrene block copolymer may be 90% or more, or 95% or more.
  • the styrene content may be 5 to 60 mass% from the viewpoint of dielectric properties in a high frequency band of 10 GHz band or higher, adhesiveness with a conductor, heat resistance, glass transition temperature and thermal expansion coefficient, It may be 5 to 50% by mass, or 10 to 40% by mass.
  • the melt flow rate (MFR) of SEPS is not particularly limited, but may be 0.1 to 130 g / 10 min under the measurement conditions of 230 ° C.
  • SEPS Sudon (registered trademark) series manufactured by Kuraray Co., Ltd., Kraton G polymer series manufactured by Kraton Polymer Japan Co., Ltd., and the like.
  • the styrene content is 20 from the viewpoint of dielectric properties in a high frequency band of 10 GHz band or higher, adhesiveness with a conductor, heat resistance, glass transition temperature and thermal expansion coefficient.
  • the amount may be up to 90% by mass, 40 to 90% by mass, 50 to 90% by mass, or 55 to 85% by mass.
  • the structural unit derived from maleic anhydride may be esterified in the styrene-maleic anhydride copolymer (SMA).
  • SMA registered trademark
  • a commercially available product may be used for each of the styrene-based thermoplastic elastomers (C).
  • the styrene content and the melt flow rate (MFR) are values described in the manufacturer's catalog or website.
  • the content of the component (C) is such that dielectric properties in a high frequency band of 10 GHz band or higher, adhesiveness with a conductor, heat resistance, glass transition temperature and heat. From the viewpoint of the coefficient of expansion, it is preferably 5 to 60 parts by mass, more preferably 10 to 60 parts by mass, and 15 to 60 parts by mass with respect to 100 parts by mass as the total of the components (A) to (C). More preferably, it is 15 to 50 parts by mass, and most preferably 15 to 40 parts by mass.
  • the content of the component (C) is 5 parts by mass or more based on 100 parts by mass of the total amount of the components (A) to (C), the dielectric property and the moisture absorption resistance in the high frequency band of 10 GHz band or more are better. If it is 60 parts by mass or less, heat resistance, moldability, processability and flame retardancy tend to be better.
  • the component (D) is not particularly limited, but examples thereof include silica, alumina, titanium oxide, mica, beryllia, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, and hydroxide. Examples thereof include magnesium, aluminum hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay (calcined clay and the like), talc, aluminum borate, silicon carbide and the like.
  • silica, alumina, mica, talc, silica, alumina, or silica may be used from the viewpoint of thermal expansion coefficient, elastic modulus, heat resistance and flame retardancy.
  • silica include precipitated silica having a high water content produced by a wet method, and dry method silica produced by a dry method and containing almost no bound water, and the like. Examples thereof include crushed silica, fumed silica, and fused silica (fused spherical silica).
  • the shape and particle size of the inorganic filler (D) are also not particularly limited.
  • the particle size may be 0.01 to 20 ⁇ m, or 0.1 to 10 ⁇ m.
  • the particle diameter refers to the average particle diameter, and is the particle diameter at a point corresponding to a volume of 50% when the cumulative frequency distribution curve based on the particle diameter is obtained with the total volume of the particles being 100%. It can be measured by a particle size distribution measuring device or the like using a laser diffraction scattering method.
  • the content of the component (D) in the resin composition is not particularly limited, but the thermal expansion coefficient, the elastic modulus, the heat resistance and the flame retardancy. From the viewpoint of properties, preferably 5 to 70 parts by mass, more preferably 15 to 70 parts by mass, further preferably 20 to 60 parts by mass, particularly preferably 35 to 60 parts by mass, relative to 100 parts by mass of the total of the resin components. , And most preferably 40 to 55 parts by mass.
  • a coupling agent may be optionally used in combination for the purpose of improving the dispersibility of the component (D) and the adhesion between the component (D) and the organic component in the resin composition.
  • the coupling agent is not particularly limited, and for example, a silane coupling agent or a titanate coupling agent can be appropriately selected and used.
  • One type of coupling agent may be used alone, or two or more types may be used in combination.
  • the amount of the coupling agent used is not particularly limited, and may be, for example, 0.1 to 5 parts by mass, or 0.5 to 3 parts by mass, relative to 100 parts by mass of the component (D). .
  • the various characteristics are less likely to deteriorate, and the features of the use of the component (D) tend to be effectively exhibited.
  • a coupling agent it is not a so-called integral blend treatment method in which the coupling agent is added after the component (D) is mixed in the resin composition, and the coupling agent is previously added to the inorganic filler by a dry method or A method using a wet surface-treated inorganic filler can be adopted. By adopting this method, the features of the component (D) can be more effectively exhibited.
  • the component (D) When the component (D) is used in the present invention, it is used as a slurry in which the component (D) is previously dispersed in an organic solvent for the purpose of improving the dispersibility of the component (D) in the resin composition.
  • the organic solvent used when the component (D) is slurried is not particularly limited, but, for example, the organic solvent exemplified in the production process of the polyphenylene ether derivative (A) described above can be applied. These may be used alone or in combination of two or more. Among these, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone can be selected from the viewpoint of dispersibility.
  • the solid content (nonvolatile content) concentration of the slurry is not particularly limited, but may be 50 to 80% by mass, or 60 to 80% by mass from the viewpoint of sedimentation and dispersibility of the inorganic filler (D). It may be% by mass.
  • the curability of the resin composition is improved, and dielectric properties, heat resistance, adhesion to conductors, elasticity in a high frequency band of 10 GHz band or higher.
  • the rate and the glass transition temperature tend to be improved.
  • the component (E) include acidic catalysts such as p-toluenesulfonic acid; amine compounds such as triethylamine, pyridine and tributylamine; methylimidazole, phenylimidazole, isocyanate mask imidazole (eg, hexamethylene diisocyanate resin and 2-ethylamine).
  • Imidazole compounds such as addition reaction products of 4-methylimidazole); tertiary amine compounds; quaternary ammonium compounds; phosphorus compounds such as triphenylphosphine; dicumyl peroxide, 2,5-dimethyl-2, 5-bis (t-butylperoxy) -3-hexyne, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, ⁇ , ⁇ ′-bis (T-butylperoxy) diisopropyl ester
  • Organic peroxides such as Zen; manganese, cobalt, etc. carboxylates of zinc, and the like.
  • these may be used alone or in combination of two or more.
  • they may be imidazole compounds, organic peroxides and carboxylates, and heat resistance, glass transition temperature, elastic modulus and thermal expansion coefficient. Therefore, the imidazole compound and the organic peroxide or carboxylate may be used in combination.
  • the organic peroxides ⁇ , ⁇ ′-bis (t-butylperoxy) diisopropylbenzene may be selected, and among the carboxylates, manganese naphthenate may be selected.
  • the content of the component (E) is not particularly limited, but is, for example, 0 with respect to 100 parts by mass of the total amount of the resin components of the present invention. 0.01 to 10 parts by mass, 0.01 to 5 parts by mass, 0.1 to 5 parts by mass, or 0.5 to 5 parts by mass. ..
  • the component (E) is used in such a range, better heat resistance and storage stability tend to be obtained.
  • the flame retardant (F) When the resin composition of the present invention contains a flame retardant (F) and, if necessary, a flame retardant aid, the flame retardancy of the resin composition tends to be improved.
  • the component (F) include phosphorus-based flame retardants, metal hydrates, halogen-based flame retardants, and the like. From the viewpoint of environmental problems, phosphorus-based flame retardants and metal hydrates may be used.
  • the flame retardant (F) one type may be used alone, or two or more types may be used in combination.
  • the phosphorus-based flame retardant is not particularly limited as long as it contains a phosphorus atom among those generally used as a flame retardant, and may be an inorganic phosphorus-based flame retardant or an organic-based flame retardant. It may be a phosphorus-based flame retardant. From the viewpoint of environmental issues, it is possible to select one that does not contain a halogen atom. From the viewpoint of dielectric properties in a high frequency band of 10 GHz band or higher, adhesiveness with a conductor, heat resistance, glass transition temperature, coefficient of thermal expansion and flame retardancy, an organic phosphorus-based flame retardant may be used.
  • inorganic phosphorus-based flame retardants include red phosphorus; ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate; inorganic nitrogen-containing phosphorus compounds such as phosphoramide. Phosphoric acid; phosphine oxide and the like.
  • organic phosphorus flame retardant include aromatic phosphoric acid ester, 1-substituted phosphonic acid diester, 2-substituted phosphinic acid ester, 2-substituted phosphinic acid metal salt, organic nitrogen-containing phosphorus compound, cyclic organic phosphorus compound, and the like. Is mentioned.
  • aromatic phosphoric acid ester compounds and metal salts of disubstituted phosphinic acids can be selected.
  • the metal salt may be any one of a lithium salt, a sodium salt, a potassium salt, a calcium salt, a magnesium salt, an aluminum salt, a titanium salt and a zinc salt, or may be an aluminum salt.
  • aromatic phosphate ester can be selected among the organic phosphorus-based flame retardants.
  • aromatic phosphoric acid ester examples include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl di-2,6-xylenyl phosphate, resorcinol bis (diphenyl phosphate), 1,3 -Phenylene bis (di-2,6-xylenyl phosphate), bisphenol A-bis (diphenyl phosphate), 1,3-phenylene bis (diphenyl phosphate), etc. may be mentioned.
  • Examples of mono-substituted phosphonic acid diesters include divinyl phenylphosphonate, diallyl phenylphosphonate, and bis (1-butenyl) phenylphosphonate.
  • Examples of the 2-substituted phosphinic acid ester include phenyl diphenylphosphinate and methyl diphenylphosphinate.
  • Examples of the metal salt of disubstituted phosphinic acid include a metal salt of dialkylphosphinic acid, a metal salt of diallylphosphinic acid, a metal salt of divinylphosphinic acid, a metal salt of diarylphosphinic acid, and the like.
  • metal salts may be any of lithium salt, sodium salt, potassium salt, calcium salt, magnesium salt, aluminum salt, titanium salt and zinc salt, and aluminum salt may be selected.
  • organic nitrogen-containing phosphorus compounds include phosphazene compounds such as bis (2-allylphenoxy) phosphazene and dicresylphosphazene; melamine phosphate; melamine pyrophosphate; melamine polyphosphate; melam polyphosphate.
  • cyclic organic phosphorus compound examples include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-10- Examples thereof include phosphaphenanthrene-10-oxide.
  • at least one kind selected from an aromatic phosphoric acid ester, a metal salt of a substituted phosphinic acid and a cyclic organic phosphorus compound may be used, and it may be selected from a metal salt of a substituted phosphinic acid and a cyclic organic phosphorus compound.
  • At least one kind thereof may be used, and a metal salt of a disubstituted phosphinic acid and a cyclic organic phosphorus compound may be used in combination.
  • the metal salt of disubstituted phosphinic acid may be a metal salt of dialkylphosphinic acid or an aluminum salt of dialkylphosphinic acid.
  • the cyclic organophosphorus compound may be 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.
  • aromatic phosphate ester may be an aromatic phosphate ester represented by the following general formula (F-1), and the metal salt of the disubstituted phosphinic acid may be represented by the following general formula (F-2).
  • R F1 to R F3 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom.
  • F1 and f2 are each independently an integer of 0 to 5, and f3 is 0 to It is an integer of 4.
  • R F4 and R F5 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms.
  • M is 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 is an integer of 1 to 4.
  • aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R F1 to R F3 the same ones as in the case of R a11 in the general formula (I) can be mentioned.
  • Both f1 and f2 may be an integer of 0 to 2 or 2.
  • f3 may be an integer of 0 to 2, may be 0 or 1, and may be 0.
  • the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R F4 and R F5 is, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group or an n-butyl group.
  • the aliphatic hydrocarbon group may be an aliphatic hydrocarbon group having 1 to 3 carbon atoms or an ethyl group.
  • Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms represented by R F4 and R F5 include a phenyl group, a naphthyl group, a biphenylyl group and an anthryl group.
  • the aromatic hydrocarbon group may be an aromatic hydrocarbon group having 6 to 10 carbon atoms.
  • y represents the valence of the metal ion, that is, it changes within the range of 1 to 4 corresponding to the type of M.
  • M may be an aluminum atom. In addition, when M is an aluminum atom, y is 3.
  • metal hydrates include aluminum hydroxide hydrate and magnesium hydroxide hydrate. These may be used alone or in combination of two or more.
  • the metal hydroxide may be an inorganic filler, but a material capable of imparting flame retardancy is classified as a flame retardant.
  • halogen-based flame retardants include chlorine-based flame retardants and bromine-based flame retardants.
  • chlorine-based flame retardant include chlorinated paraffin and the like.
  • brominated flame retardant include brominated epoxy resins such as brominated bisphenol A type epoxy resin and brominated phenol novolac type epoxy resin; hexabromobenzene, pentabromotoluene, ethylenebis (pentabromophenyl), ethylenebistetra Bromophthalimide, 1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis (tribromophenoxy) ethane, brominated polyphenylene ether, brominated polystyrene, 2, Brominated addition type flame retardants such as 4,6-tris (tribromoph
  • Bromination reaction type flame retardants containing unsaturated double bond groups such as bromophenyl maleimide, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromobisphenol A type dimethacrylate, pentabromobenzyl acrylate, brominated styrene (here, The “reactive type” refers to a polymer in which bromine is introduced in a chemically bonded form) and the like. These may be used alone or in combination of two or more.
  • the content of the phosphorus-based flame retardant in the resin composition is not particularly limited. Is preferably 0.2 to 5 parts by mass, more preferably 0.3 to 3 parts by mass, and more preferably 0.5 to 5 parts by mass in terms of phosphorus atom, based on 100 parts by mass of the total resin components. It is more preferably about 3 to 3 parts by mass. When the phosphorus atom content is 0.2 parts by mass or more, better flame retardancy tends to be obtained.
  • the content of phosphorus atoms is 5 parts by mass or less, better moldability, high adhesiveness with a conductor, excellent heat resistance, and high glass transition temperature tend to be obtained.
  • the resin composition of the present invention contains a halogen-based flame retardant, it is preferably 20 parts by mass or less based on 100 parts by mass of the total resin components from the viewpoint of environmental problems and chemical resistance. It is more preferably not more than 5 parts by mass, further preferably not more than 5 parts by mass, particularly preferably not more than 3 parts by mass.
  • the component (F) a mode in which a halogen-based flame retardant is not used is also preferable.
  • the resin composition of the present invention contains a flame retardant other than the phosphorus-based flame retardant, it is not particularly limited, but is 0.5 to 20 parts by mass relative to 100 parts by mass of the total resin components. The amount may be 1 to 15 parts by mass, 1 to 10 parts by mass, or 2 to 8 parts by mass.
  • the resin composition of the present invention may contain a flame retardant aid, for example, an inorganic flame retardant aid such as antimony trioxide or zinc molybdate.
  • a flame retardant aid for example, an inorganic flame retardant aid such as antimony trioxide or zinc molybdate.
  • its content is not particularly limited, but for example, it is 0.1 to 20 parts by mass with respect to 100 parts by mass of the total resin components. The amount may be 0.1 to 10 parts by mass. When the flame retardant aid is used in such a range, better chemical resistance tends to be obtained.
  • Crosslinking agent (G) By incorporating the crosslinking agent (G) into the resin composition of the present invention, the reaction between the component (A) and the component (B) tends to be promoted.
  • the cross-linking agent (G) is not particularly limited as long as it can cross-link with the components (A) and (B), but it is a group capable of reacting with the carbon-carbon double bond of the maleimide group. It is preferable that the compound has Among them, the crosslinking agent (G) is preferably a crosslinking agent having two or more ethylenically unsaturated bonds.
  • Examples of the ethylenically unsaturated bond include unsaturated aliphatic hydrocarbon groups such as vinyl group, isopropenyl group, allyl group, 1-methylallyl group and 3-butenyl group; maleimide group, (meth) acryloyl group and the like.
  • An unsaturated bond contained in a substituent containing a hetero atom and the like can be mentioned.
  • the cross-linking agent (G) those having an ethylenic unsaturated bond as the unsaturated aliphatic hydrocarbon group are preferable, and those having a vinyl group are more preferable, from the viewpoint of dielectric properties in a high frequency band of 10 GHz or higher.
  • the number of ethylenically unsaturated bonds that the cross-linking agent (G) has in one molecule is preferably 3 or more, more preferably 5 or more, and further preferably 10 or more from the viewpoint of obtaining excellent heat resistance. .
  • cross-linking agent (G) examples include unsaturated polyester; polybutadiene having a carbon-carbon double bond in its side chain, carbon in its side chain such as polyisoprene having a carbon-carbon double bond in its side chain.
  • a polyalkadiene having a carbon double bond a polyvinyl compound such as divinylbenzene and divinylbiphenyl; a poly (meth) acrylate compound; a polyallyl compound such as triallyl cyanurate and triallyl isocyanurate; a polyamine compound such as diaminodiphenylmethane Can be mentioned.
  • polyalkadienes having a carbon-carbon double bond in the side chain are preferable, and polybutadiene having a carbon-carbon double bond in the side chain is more preferable.
  • the crosslinking agent one type may be used alone, or two or more types may be used in combination.
  • the resin composition of the present invention may further contain a resin material such as a thermoplastic resin and an elastomer (excluding the component (C)), a coupling agent, an antioxidant, a heat stabilizer, and an antistatic agent, if necessary.
  • a resin material such as a thermoplastic resin and an elastomer (excluding the component (C))
  • a coupling agent such as a thermoplastic resin and an elastomer (excluding the component (C)
  • a coupling agent such as a thermoplastic resin and an elastomer (excluding the component (C)
  • an antioxidant excluding the component (C)
  • an antistatic agent if necessary.
  • Agents, ultraviolet absorbers, pigments, colorants, lubricants and the like can be appropriately selected and contained. These may be used alone or in combination of two or more. Further, the amount of these used is not particularly limited, and may be used within a range that does not impair the effects of the present invention.
  • the resin composition of the present invention may contain an organic solvent from the viewpoint of facilitating the handling by diluting and facilitating the production of a prepreg described later.
  • the resin composition containing an organic solvent is generally referred to as a resin varnish or a varnish.
  • the organic solvent is not particularly limited, but examples thereof include alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve and propylene glycol monomethyl ether; ketone type solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; tetrahydrofuran.
  • Ether solvent such as; aromatic solvent such as toluene, xylene, mesitylene; nitrogen atom-containing solvent such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone; sulfur atom-containing solvent such as dimethyl sulfoxide; ester such as ⁇ -butyrolactone
  • system solvents include system solvents.
  • alcohol-based solvent, ketone-based solvent may be a nitrogen atom-containing solvent, may be a ketone-based solvent, acetone, methyl ethyl ketone, methyl isobutyl ketone, even cyclohexanone Well, it may be methyl ethyl ketone.
  • the organic solvent one type may be used alone, or two or more types may be used in combination.
  • the content of the organic solvent in the resin composition of the present invention is not particularly limited, but the solid content concentration may be 30 to 90% by mass, 40 to 80% by mass, or 40 to 70% by mass. It may be mass% or may be 40 to 60 mass%.
  • the handling becomes easy, the impregnation into the substrate and the appearance of the prepreg produced are good, and the solid content of the resin in the prepreg described below. It tends to be easier to adjust the concentration, and it becomes easier to manufacture a prepreg having a desired thickness.
  • the resin composition of the present invention can be obtained by mixing the above-mentioned components (A) and (B), other components used in combination if necessary, and, if necessary, an organic solvent by a known method. At this time, it may be dissolved or dispersed while stirring. Conditions such as mixing order, temperature, time, etc. are not particularly limited and can be set arbitrarily.
  • the resin composition of the present invention has good compatibility, and there is a tendency that precipitates do not occur even if left for one day. Further, in a more excellent compatibility mode, there is a tendency that precipitates do not occur even if left for one week (however, phase separation may occur), and in a more excellent compatibility mode, Even if left for one week, there is a tendency that even phase separation does not occur.
  • the cured product of the resin composition of the present invention (a laminate and a resin film that does not include a fiber base material such as glass cloth) tends to have a dielectric constant (Dk) of 2.90 or less at 10 GHz, and more preferable one is 2.80 or less, and more preferably 2.75 or less.
  • the dielectric loss tangent (Df) at 10 GHz tends to be 0.0055 or less.
  • the lower limit of the dielectric constant (Dk) at 10 GHz is not particularly limited, but tends to be 2.4 or more, and may be 2.6 or more.
  • the lower limit of the dielectric loss tangent (Df) at 10 GHz is not particularly limited, but tends to be 0.0015 or more, and may be 0.0020 or more, or 0.0023 or more.
  • the dielectric loss tangent (Df) at 10 GHz is 0.0050 or less, 0.0045 or less, 0.0035 or less, 0.0030 or less, and 0.0029 or less.
  • the dielectric constant and the dielectric loss tangent are values measured by the cavity resonator method, and more specifically, values measured by the method described in Examples. Further, when simply referred to as a dielectric constant, it means a relative dielectric constant.
  • the present invention also provides a prepreg containing the resin composition of the present invention. More specifically, the prepreg comprises the resin composition of the present invention and a sheet-shaped fiber reinforced substrate, and the sheet-shaped fiber reinforced substrate is impregnated or coated with the resin composition of the present invention. Then, it can be manufactured by drying. More specifically, for example, the prepreg of the present invention can be produced by heating and drying in a drying oven at a temperature of usually 80 to 200 ° C. for 1 to 30 minutes and semi-curing (B-stage). .
  • the amount of the resin composition used is such that the solid content concentration derived from the resin composition in the prepreg after drying is preferably 30 to 90% by mass, more preferably 50 to 90% by mass, and further preferably 65 to 80% by mass. Can be determined. When the solid content concentration is within the above range, a better moldability tends to be obtained when the laminate is used.
  • the sheet-shaped fiber-reinforced base material of the prepreg known materials used for various laminated plates for electrical insulating materials are used.
  • the material of the sheet-like reinforcing base material include inorganic fibers such as E glass, D glass, S glass, and Q glass; organic fibers such as polyimide, polyester, and tetrafluoroethylene; and a mixture thereof.
  • These sheet-like reinforcing base materials have, for example, woven cloth, non-woven cloth, robink, chopped strand mat, surfacing mat and the like.
  • the thickness of the sheet-shaped fiber-reinforced base material is not particularly limited, and for example, one having a thickness of 0.02 to 0.5 mm can be used. Further, from the viewpoints of impregnation of the resin composition, heat resistance when formed into a laminated plate, moisture absorption resistance, and processability, those surface-treated with a coupling agent or the like, and those mechanically opened. Can be used.
  • the hot melt method is a method in which an organic solvent is not contained in a resin composition, and (1) a coated paper having good releasability from the resin composition is once coated and laminated on a sheet-like reinforcing base material, or (2) A method in which a sheet-shaped reinforcing base material is directly coated with a die coater.
  • the solvent method the resin composition is allowed to contain an organic solvent, the sheet-shaped reinforcing base material is immersed in the obtained resin composition, the sheet-shaped reinforcing base material is impregnated, and then dried. Is the way.
  • the present invention also provides a resin film containing the resin composition of the present invention.
  • the resin film can be produced by applying a resin composition containing an organic solvent, that is, a resin varnish to a support and heating and drying.
  • the support include polyolefin films such as polyethylene, polypropylene and polyvinyl chloride; polyester films such as polyethylene terephthalate (hereinafter also referred to as “PET”) and polyethylene naphthalate; various plastics such as polycarbonate films and polyimide films. Examples include films.
  • PET polyethylene terephthalate
  • plastics such as polycarbonate films and polyimide films. Examples include films.
  • a metal foil such as a copper foil or an aluminum foil, a release paper, etc. may be used as the support.
  • the support may be subjected to surface treatment such as matte treatment and corona treatment. Further, the support may be subjected to a release treatment with a silicone resin-based release agent, an alkyd resin-based release agent, a fluororesin-based release agent, or the like.
  • the thickness of the support is not particularly limited, but is preferably 10 to 150 ⁇ m, more preferably 25 to 50 ⁇ m.
  • the method of applying the resin varnish to the support is not particularly limited, and for example, a coating device known to those skilled in the art such as a comma coater, a bar coater, a kiss coater, a roll coater, a gravure coater, or a die coater can be used. These coating devices may be appropriately selected depending on the film thickness.
  • the drying temperature and the drying time may be appropriately determined according to the amount of the organic solvent used, the boiling point of the organic solvent used, and the like. For example, in the case of a resin varnish containing about 40 to 60 mass% of the organic solvent, 50
  • the resin film can be suitably formed by drying at about 150 ° C. for about 3 to 10 minutes.
  • Laminate It is also possible to produce a laminated plate containing the prepreg of the present invention and a metal foil. Specifically, a metal foil is placed on one or both sides of one prepreg of the present invention, or a metal foil is placed on one or both sides of a prepreg obtained by stacking two or more prepregs of the present invention, and then heated. A laminated plate can be obtained by pressure molding. The laminated plate on which the metal foil is arranged may be referred to as a metal-clad laminated plate.
  • the metal of the metal foil is not particularly limited as long as it is used for electrical insulating materials, but from the viewpoint of conductivity, copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium. , Chromium, or an alloy containing at least one of these metal elements, copper or aluminum, and preferably copper.
  • the conditions of the heat and pressure molding are not particularly limited, but for example, the temperature may be 100 ° C. to 300 ° C., the pressure may be 0.2 to 10 MPa, and the time may be 0.1 to 5 hours. .. Further, the heat and pressure molding may be carried out by using a vacuum press or the like for holding the vacuum state for 0.5 to 5 hours.
  • the multilayer printed wiring board of the present invention contains at least one selected from the group consisting of the prepreg of the present invention, the resin film of the present invention, and the laminate of the present invention.
  • the multilayer printed wiring board of the present invention is perforated, metal-plated by a known method using at least one selected from the group consisting of the prepreg of the present invention, the resin film of the present invention and the laminate of the present invention.
  • a multilayer printed wiring board can be manufactured by performing processing, circuit formation processing such as etching of metal foil, and multilayer adhesion processing.
  • the resin composition, prepreg, laminated board, resin film and multilayer printed wiring board of the present invention can be suitably used for electronic devices handling high frequency signals of 10 GHz or higher.
  • the multilayer printed wiring board is useful as a multilayer printed wiring board for millimeter wave radar.
  • the number average molecular weight was measured as follows. (Measurement method of number average molecular weight) It was converted from a calibration curve using standard polystyrene by gel permeation chromatography (GPC). The calibration curve is based on standard polystyrene: TSKstandard POLYSTYRENE (Type; A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) [manufactured by Tosoh Corporation, It was approximated by a cubic equation using the product name]. The measurement conditions of GPC are shown below.
  • Production of polyphenylene ether derivative (A-3) By carrying out the same procedure as in Production Example A-1, except that diallylbisphenol A (DABPA) was used instead of 2-allylphenol, and the amounts of the components used were as shown in Table 1, A polyphenylene ether derivative (A-3) having an organic group in which two allyl groups were substituted at one end of the molecule was obtained. The number average molecular weight of the polyphenylene ether compound was 4,300.
  • DABPA diallylbisphenol A
  • Production Example A-5 Production of polyphenylene ether derivative (A-5)]
  • an allyl group-containing compound represented by the following general formula (1) hereinafter sometimes referred to as tetraallyl bisphenols
  • each of the components is A polyphenylene ether derivative (A-5) having an organic group substituted with four allyl groups at the end of a molecule was obtained by performing the same operation except that the amount used was as shown in Table 1.
  • the number average molecular weight of the polyphenylene ether compound was 5,400.
  • X a2 is an organic group and is described in the same manner as X a2 in the general formula (a-5).
  • Production Example A-7 Production of polyphenylene ether derivative (A-7)] The same as in Production Example A-5 except that "Zylon (registered trademark) S202A” (trade name, manufactured by Asahi Kasei Corporation) was changed to "Zylon (registered trademark) S203A” (trade name, manufactured by Asahi Kasei Corporation). By performing the operation, a polyphenylene ether derivative (A-7) having an organic group in which four allyl groups were substituted at the terminal of a molecule was obtained. The number average molecular weight of the polyphenylene ether compound was 4,200.
  • Production Example A-8 Production of polyphenylene ether derivative (A-8)] The same procedure as in Production Example A-7 was repeated except that the amount of the allyl group-containing compound represented by the following general formula (1) was changed as shown in Table 1. A polyphenylene ether derivative (A-8) having an organic group in which four groups were substituted was obtained. The number average molecular weight of the polyphenylene ether compound was 3,800.
  • reaction solution taken out a small amount of methanol / benzene mixed solvent (weight ratio 1: 1) was added dropwise, was subjected to FT-IR measurement of solids were purified by reprecipitation, 3,400 cm -1 vicinity of The appearance of peaks derived from primary amino groups was confirmed.
  • BMI-4000 (trade name, manufactured by Daiwa Kasei Kogyo Co., Ltd.) and propylene glycol monomethyl ether were added to the above reaction solution, the liquid temperature was raised with stirring, and the reaction was carried out for 4 hours while keeping the temperature at 100 ° C.
  • the polyphenylene ether derivative (A′-9) was manufactured by cooling and filtering through a 200 mesh filter. A small amount of this reaction solution was taken out, and FT-IR measurement was performed on the solid obtained by reprecipitation and purification in the same manner as above. The disappearance of the primary amino group-derived peak near 3,500 cm ⁇ 1 and 1,700 to 1,730 cm The appearance of a carbonyl group of -1 was confirmed. The number average molecular weight of this solid substance was about 6,500.
  • the amount of each component used is shown in Table 1.
  • Each material in Table 1 is as follows.
  • diallyl bisphenol A 2,2-bis (3-allyl-4-hydroxyphenyl) ) Propane, manufactured by Daiwa Kasei Kogyo Co., Ltd.
  • tetraallyl bisphenols compounds represented by the following general formula (1), manufactured by Gunei Chemical Industry Co., Ltd.
  • X a2 is an organic group, and it is described in the same manner as the X a2 in the general formula (a-5).
  • -P-aminophenol manufactured by Ihara Chemical Industry Co., Ltd.
  • Each material in Table 2 is as follows.
  • Examples 1 to 8 and Comparative Examples 1 and 2 Each component shown in Table 3 was stirred and mixed while heating at room temperature or 50 to 80 ° C. according to the blending amount (unit: parts by mass) shown in Table 3 to obtain a solid (nonvolatile) concentration of about 50% by mass.
  • a resin composition was prepared. The resin composition obtained in each example was applied to a 0.07 mm-thick glass cloth (NE glass, manufactured by Nitto Boseki Co., Ltd.) and then dried by heating at 105 ° C. for 5 minutes to give a resin content (resin component). Amount of about 73 mass% of prepreg was prepared.
  • a double-sided copper-clad laminate (thickness: 0.8 mm) was produced by heat-press molding under conditions of a temperature of 230 ° C., a pressure of 4 MPa, and a time of 180 minutes.
  • the resin compositions obtained in each example were visually observed, and the compatibility (the presence or absence of macroscopic (macro) phase separation and precipitates) was evaluated according to the following criteria.
  • the evaluations A to C are preferable, A or B is more preferable, and A is further preferable.
  • B There was no change when left for 1 day, but when left for 1 week or longer, there was no precipitate, but some macroscopic phase separation occurred.
  • C When left for one day, there was no precipitate, but macroscopic phase separation occurred.
  • D After standing for 1 day, a precipitate was confirmed.
  • the resin was put into a Teflon (registered trademark) sheet that was crushed and die-cut into a size of 1 mm and a size of 50 mm ⁇ 35 mm.
  • a foil (BF-ANP18, manufactured by Furukawa Electric Co., Ltd.) is arranged so that the M surface is in contact with it, and heat-pressed under conditions of a temperature of 230 ° C., a pressure of 2.0 MPa and a time of 120 minutes, and a double-sided copper clad laminate. (Thickness: 1 mm) was produced.
  • a double-sided copper clad laminate thus obtained was immersed in a copper etching solution containing ammonium persulfate (manufactured by Mitsubishi Gas Chemical Co., Inc.) 10% by mass to remove the copper foil, and then a 2 mm ⁇ 50 mm evaluation substrate was obtained. It was made.
  • the evaluation board Using the evaluation board, the dielectric constant (Dk) and the dielectric loss tangent (Df) in the 10 GHz band were calculated from the resonance frequency and the unloaded Q value obtained by the cavity resonator method.
  • the dielectric constant (Dk) is preferably 2.90 or less, more preferably 2.75 or less.
  • the dielectric loss tangent (Df) is preferably 0.0055 or less, more preferably 0.0050 or less, and further preferably 0.0045 or less.
  • each material in Table 3 is as follows.
  • SA9000 methacryl-modified polyphenylene ether derivative modified at both ends represented by the following formula (2), weight average molecular weight 1,700 (SABIC Innovative Plastics, trade name) (In the formula (2), x1 and x2 are each independently 0 to 20. The total of x1 and x2 is preferably 1 to 30.)
  • the compatibility of the resin composition is good or excellent, and the copper-clad laminate produced using these has a compatibility of 10 GHz band or higher. Has excellent dielectric characteristics in the high frequency band.
  • Comparative Example 1 the compatibility of the resin composition is poor and the dielectric properties in the high frequency band of 10 GHz band or higher are also insufficient.
  • Comparative Example 2 although the compatibility of the resin composition was good, the copper-clad laminate had poor dielectric properties in the high frequency band of 10 GHz band or higher.
  • the resin composition of the present invention has good compatibility, and since the laminated plate produced from the resin composition has excellent dielectric properties especially in a high frequency band of 10 GHz band or higher, radio waves in a frequency band exceeding 6 GHz are used. It is useful for a fifth-generation mobile communication system (5G) antenna and a multilayer printed wiring board used for a millimeter-wave radar that uses radio waves in the frequency band of 30 to 300 GHz.
  • 5G fifth-generation mobile communication system
  • millimeter-wave radar uses radio waves in the frequency band of 30 to 300 GHz.

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Abstract

Provided are: a resin composition capable of exhibiting excellent dielectric properties in the 10-GHz band and higher-frequency bands; a cured object obtained from the resin composition; a prepreg; a laminate; a resin film; a multilayered printed wiring board; a multilayered printed wiring board for millimeter-wave radars; and a poly(phenylene ether) derivative rendering such resin composition obtainable. Specifically, the resin composition comprises (A) a poly(phenylene ether) derivative including an organic group substituted by an unsaturated aliphatic hydrocarbon group and (B) at least one compound selected from the group consisting of maleimide compounds having at least two N-substituted maleimide groups and derivatives of the maleimide compounds.

Description

樹脂組成物、樹脂組成物の硬化物、プリプレグ、積層板、樹脂フィルム、多層プリント配線板、ミリ波レーダー用多層プリント配線板及びポリフェニレンエーテル誘導体Resin composition, cured product of resin composition, prepreg, laminate, resin film, multilayer printed wiring board, multilayer printed wiring board for millimeter-wave radar, and polyphenylene ether derivative
　本発明は、樹脂組成物、樹脂組成物の硬化物、プリプレグ、積層板、樹脂フィルム、多層プリント配線板、ミリ波レーダー用多層プリント配線板及びポリフェニレンエーテル誘導体に関する。 The present invention relates to a resin composition, a cured product of the resin composition, a prepreg, a laminate, a resin film, a multilayer printed wiring board, a multilayer printed wiring board for millimeter wave radar, and a polyphenylene ether derivative.
　携帯電話に代表される移動体通信機器、その基地局装置、サーバー、ルーター等のネットワークインフラ機器、又は大型コンピュータ等では、使用する信号の高速化及び大容量化が年々進んでいる。これに伴い、これらの電子機器に搭載されるプリント配線板には高周波化対応が必要となり、伝送損失の低減を可能とする高周波数帯における誘電特性（低誘電率及び低誘電正接；以下、高周波特性と称することがある。）に優れる基板材料が求められている。近年、このような高周波信号を扱うアプリケーションとして、上述した電子機器のほかに、ＩＴＳ分野（自動車、交通システム関連）及び室内の近距離通信分野でも高周波無線信号を扱う新規システムの実用化又は実用計画が進んでおり、今後、これらの機器に搭載するプリント配線板に対しても、低伝送損失基板材料がさらに要求されると予想される。 In mobile communication devices typified by mobile phones, their base station devices, servers, network infrastructure devices such as routers, and large computers, the speed and capacity of signals used are increasing year by year. Along with this, printed wiring boards mounted on these electronic devices are required to support high frequencies, and dielectric characteristics (low dielectric constant and low dielectric loss tangent in the high frequency band that enable reduction of transmission loss; hereinafter referred to as high frequency). There is a demand for a substrate material having excellent characteristics. In recent years, as an application for handling such high frequency signals, in addition to the above-mentioned electronic devices, a new system for handling high frequency radio signals in the ITS field (related to automobiles and transportation systems) and indoor short-distance communication field is put into practical use or a practical plan. It is expected that further low transmission loss substrate materials will be required for printed wiring boards mounted on these devices in the future.
　従来、低伝送損失が要求されるプリント配線板には、高周波特性に優れる耐熱性熱可塑性ポリマーとしてポリフェニレンエーテル（ＰＰＥ）系樹脂が使用されてきた。例えば、ポリフェニレンエーテルと熱硬化性樹脂とを併用する方法が提案されている。具体的には、ポリフェニレンエーテルとエポキシ樹脂を含有する樹脂組成物（例えば、特許文献１参照）、ポリフェニレンエーテルと熱硬化性樹脂の中でも誘電率が低いシアネート樹脂を含有する樹脂組成物（例えば、特許文献２参照）等が開示されている。
　しかしながら、上記特許文献１～２に記載の樹脂組成物は、ＧＨｚ領域における高周波特性、導体との接着性、低熱膨張係数、難燃性が総合的に不十分であったり、ポリフェニレンエーテルと熱硬化性樹脂との相容性が低いことにより耐熱性が低下することがあった。 Conventionally, a polyphenylene ether (PPE) resin has been used as a heat-resistant thermoplastic polymer having excellent high-frequency characteristics for a printed wiring board that requires low transmission loss. For example, a method of using polyphenylene ether and a thermosetting resin in combination has been proposed. Specifically, a resin composition containing a polyphenylene ether and an epoxy resin (see, for example, Patent Document 1), a resin composition containing a polyphenylene ether and a cyanate resin having a low dielectric constant among thermosetting resins (for example, patents Reference 2) and the like are disclosed.
However, the resin compositions described in Patent Documents 1 and 2 described above are generally insufficient in high-frequency characteristics in the GHz range, adhesiveness with conductors, low coefficient of thermal expansion, flame retardancy, and polyphenylene ether and thermosetting. In some cases, the heat resistance may decrease due to the low compatibility with the resin.
　このような状況下、特に相容性が良好で、且つ高周波数帯における誘電特性、導体との高接着性、優れた耐熱性、高ガラス転移温度、低熱膨張係数及び高難燃性を有する樹脂組成物を提供することを課題として、１分子中にＮ－置換マレイミド構造含有基及び下記一般式で表される構造単位を有するポリフェニレンエーテル誘導体（Ａ）、エポキシ樹脂、シアネート樹脂及びマレイミド化合物からなる群より選ばれる少なくとも１種類の熱硬化性樹脂（Ｂ）、及びスチレン系熱可塑性エラストマー（Ｃ）を含む樹脂組成物が提案されている（例えば、特許文献３参照）。
Figure JPOXMLDOC01-appb-C000006
（式中、Ｒ１は各々独立に、炭素数１～５の脂肪族炭化水素基又はハロゲン原子である。ｘは０～４の整数である。） Under such circumstances, a resin having particularly good compatibility and having dielectric properties in a high frequency band, high adhesion with a conductor, excellent heat resistance, high glass transition temperature, low thermal expansion coefficient and high flame retardancy. With the object of providing a composition, it is composed of a polyphenylene ether derivative (A) having an N-substituted maleimide structure-containing group and a structural unit represented by the following general formula in one molecule, an epoxy resin, a cyanate resin and a maleimide compound. A resin composition containing at least one thermosetting resin (B) selected from the group and a styrene-based thermoplastic elastomer (C) has been proposed (see, for example, Patent Document 3).
Figure JPOXMLDOC01-appb-C000006
(In the formula, each R 1 is independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. X is an integer of 0 to 4.)
特開昭５８－０６９０４６号公報JP 58-069046 A 特公昭６１－０１８９３７号公報Japanese Patent Publication No. 61-018937 国際公開第２０１６／１７５３２６号International Publication No. 2016/175326
　特許文献３に記載の樹脂組成物は、確かに高周波数帯における誘電特性にも優れる結果となっているが、近年は、６ＧＨｚを超える周波数帯の電波が使用される第五世代移動通信システム（５Ｇ）アンテナ及び３０～３００ＧＨｚの周波数帯の電波が使用されるミリ波レーダー等にも利用可能な、高周波数帯における誘電特性がさらに改善された樹脂組成物の開発が切望されており、新規な材料の開発が急務となっている。 Although the resin composition described in Patent Document 3 is surely excellent in the dielectric property in a high frequency band, in recent years, a fifth generation mobile communication system using radio waves in a frequency band exceeding 6 GHz ( 5G) Development of a resin composition having improved dielectric characteristics in a high frequency band, which can be used also for a millimeter wave radar in which an antenna and a radio wave in a frequency band of 30 to 300 GHz are used, has been earnestly desired, and a new resin composition has been desired. Material development is an urgent task.
　本発明は、このような現状に鑑み、１０ＧＨｚ帯以上の高周波数帯において優れた誘電特性を発現し得る樹脂組成物、該樹脂組成物の硬化物、プリプレグ、樹脂フィルム、多層プリント配線板及びミリ波レーダー用多層プリント配線板、並びに、そのような樹脂組成物を得ることが可能となるポリフェニレンエーテル誘導体を提供することを課題とする。 In view of such circumstances, the present invention provides a resin composition capable of exhibiting excellent dielectric properties in a high frequency band of 10 GHz or higher, a cured product of the resin composition, a prepreg, a resin film, a multilayer printed wiring board, and a millimeter. It is an object of the present invention to provide a multilayer printed wiring board for wave radar, and a polyphenylene ether derivative that makes it possible to obtain such a resin composition.
　本発明者らは、上記課題を解決するために鋭意研究を重ねた結果、特定の分子構造を有するポリフェニレンエーテル誘導体と、特定のマレイミド化合物及びその誘導体からなる群から選択される少なくとも１種類とを含有する樹脂組成物であれば、１０ＧＨｚ帯以上の高周波数帯において優れた誘電特性を発現することを見出し、本発明を完成するに至った。
　すなわち、本発明は、下記［１］～［２０］に関するものである。 The present inventors have conducted extensive studies in order to solve the above problems, as a result, a polyphenylene ether derivative having a specific molecular structure, and at least one selected from the group consisting of a specific maleimide compound and its derivative. It has been found that the resin composition containing the compound exhibits excellent dielectric properties in a high frequency band of 10 GHz or higher, and has completed the present invention.
That is, the present invention relates to the following [1] to [20].
［１］（Ａ）不飽和脂肪族炭化水素基が置換した有機基を有するポリフェニレンエーテル誘導体、及び
　（Ｂ）Ｎ－置換マレイミド基を少なくとも２個有するマレイミド化合物及びその誘導体からなる群から選択される少なくとも１種類、
を含有してなる、樹脂組成物。
［２］前記（Ａ）成分が有する不飽和脂肪族炭化水素基が置換した有機基が下記一般式（ａ－１）で表される構造を有する、上記［１］に記載の樹脂組成物。
Figure JPOXMLDOC01-appb-C000007
（式（ａ－１）中、Ｒａ１は炭素数２～１０の不飽和脂肪族炭化水素基である。ｍ１は１又は２であり、ｎ１は０又は１である。＊は、他の構造への結合位置を示す。）
［３］前記（Ａ）成分が有する不飽和脂肪族炭化水素基が置換した有機基が下記一般式（ａ－２）で表される構造を有する、上記［１］又は［２］に記載の樹脂組成物。
Figure JPOXMLDOC01-appb-C000008
（式（ａ－２）中、Ｒａ２及びＲａ３は、各々独立に、炭素数２～１０の不飽和脂肪族炭化水素基である。＊は、他の構造への結合位置を示す。）
［４］前記（Ａ）成分が有する不飽和脂肪族炭化水素基の合計数が２つ以上である、上記［１］～［３］のいずれかに記載の樹脂組成物。
［５］前記（Ａ）成分が有する不飽和脂肪族炭化水素基の合計数が４つ以上である、上記［１］～［４］のいずれかに記載の樹脂組成物。
［６］前記（Ａ）成分において、前記不飽和脂肪族炭化水素基が、ビニル基、イソプロペニル基、アリル基、１－メチルアリル基又は３－ブテニル基である、上記［１］～［５］のいずれかに記載の樹脂組成物。
［７］前記（Ｂ）成分が、Ｎ－置換マレイミド基を少なくとも２個有するマレイミド化合物（ｂ１）由来の構造単位とジアミン化合物（ｂ２）由来の構造単位とを有する、上記［１］～［６］のいずれかに記載の樹脂組成物。
［８］前記（Ｂ）成分が、下記一般式（Ｂ－１）で表されるポリアミノビスマレイミド化合物を含む、上記［１］～［７］のいずれかに記載の樹脂組成物。
Figure JPOXMLDOC01-appb-C000009
（式（Ｂ－１）中、ＸＢ１及びＸＢ２は、各々独立に、有機基である。）
［９］１０ＧＨｚにおける誘電率が２．９０以下であり、且つ１０ＧＨｚにおける誘電正接が０．００５５以下である、上記［１］～［８］のいずれかに記載の樹脂組成物の硬化物。
［１０］上記［１］～［８］のいずれかに記載の樹脂組成物を含有してなるプリプレグ。
［１１］上記［１０］に記載のプリプレグと金属箔とを含有してなる積層板。
［１２］上記［１］～［８］のいずれかに記載の樹脂組成物を含有してなる樹脂フィルム。
［１３］上記［１０］に記載のプリプレグ、上記［１１］に記載の積層板及び上記［１２］に記載の樹脂フィルムからなる群から選択される少なくとも１種類を含有してなる多層プリント配線板。
［１４］上記［１０］に記載のプリプレグ、上記［１１］に記載の積層板及び上記［１２］に記載の樹脂フィルムからなる群から選択される少なくとも１種類を含有してなるミリ波レーダー用多層プリント配線板。
［１５］不飽和脂肪族炭化水素基が置換した有機基を有するポリフェニレンエーテル誘導体。
［１６］前記不飽和脂肪族炭化水素基が置換した有機基が下記一般式（ａ－１）で表される構造を有する、上記［１５］に記載のポリフェニレンエーテル誘導体。
Figure JPOXMLDOC01-appb-C000010
（式（ａ－１）中、Ｒａ１は炭素数２～１０の不飽和脂肪族炭化水素基である。ｍ１は１又は２であり、ｎ１は０又は１である。＊は、他の構造への結合位置を示す。）
［１７］前記不飽和脂肪族炭化水素基が置換した有機基が下記一般式（ａ－２）で表される構造を有する、上記［１５］又は［１６］に記載のポリフェニレンエーテル誘導体。
Figure JPOXMLDOC01-appb-C000011
（式（ａ－２）中、Ｒａ２及びＲａ３は、各々独立に、炭素数２～１０の不飽和脂肪族炭化水素基である。＊は、他の構造への結合位置を示す。）
［１８］前記不飽和脂肪族炭化水素基の合計数が２つ以上である、上記［１５］～［１７］のいずれかに記載のポリフェニレンエーテル誘導体。
［１９］前記不飽和脂肪族炭化水素基の合計数が４つ以上である、上記［１５］～［１８］のいずれかに記載のポリフェニレンエーテル誘導体。
［２０］前記不飽和脂肪族炭化水素基が、ビニル基、イソプロペニル基、アリル基、１－メチルアリル基又は３－ブテニル基である、上記［１５］～［１９］のいずれかに記載のポリフェニレンエーテル誘導体。 [1] selected from the group consisting of (A) a polyphenylene ether derivative having an organic group substituted with an unsaturated aliphatic hydrocarbon group, and (B) a maleimide compound having at least two N-substituted maleimide groups and a derivative thereof. At least one kind,
A resin composition comprising:
[2] The resin composition according to the above [1], wherein the organic group substituted by the unsaturated aliphatic hydrocarbon group contained in the component (A) has a structure represented by the following general formula (a-1).
Figure JPOXMLDOC01-appb-C000007
(In the formula (a-1), R a1 is an unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms. M1 is 1 or 2, n1 is 0 or 1. * represents another structure. The binding position to is shown.)
[3] The above [1] or [2], wherein the unsaturated aliphatic hydrocarbon group-substituted organic group in the component (A) has a structure represented by the following general formula (a-2). Resin composition.
Figure JPOXMLDOC01-appb-C000008
(In the formula (a-2), R a2 and R a3 are each independently an unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms. * Indicates a bonding position to another structure.)
[4] The resin composition according to any one of the above [1] to [3], wherein the total number of unsaturated aliphatic hydrocarbon groups contained in the component (A) is 2 or more.
[5] The resin composition according to any one of the above [1] to [4], wherein the total number of unsaturated aliphatic hydrocarbon groups contained in the component (A) is 4 or more.
[6] In the component (A), the unsaturated aliphatic hydrocarbon group is a vinyl group, an isopropenyl group, an allyl group, a 1-methylallyl group or a 3-butenyl group, and the above [1] to [5] The resin composition according to any one of 1.
[7] The above-mentioned [1] to [6], wherein the component (B) has a structural unit derived from a maleimide compound (b1) having at least two N-substituted maleimide groups and a structural unit derived from a diamine compound (b2). ] The resin composition in any one of these.
[8] The resin composition according to any one of the above [1] to [7], wherein the component (B) contains a polyamino bismaleimide compound represented by the following general formula (B-1).
Figure JPOXMLDOC01-appb-C000009
(In formula (B-1), X B1 and X B2 are each independently an organic group.)
[9] A cured product of the resin composition according to any one of the above [1] to [8], which has a dielectric constant at 10 GHz of 2.90 or less and a dielectric loss tangent at 10 GHz of 0.0055 or less.
[10] A prepreg containing the resin composition according to any one of the above [1] to [8].
[11] A laminated board containing the prepreg according to the above [10] and a metal foil.
[12] A resin film containing the resin composition according to any one of the above [1] to [8].
[13] A multilayer printed wiring board containing at least one selected from the group consisting of the prepreg described in [10] above, the laminated board described in [11] above, and the resin film described in [12] above. ..
[14] A millimeter wave radar including at least one selected from the group consisting of the prepreg described in [10] above, the laminated plate described in [11] above and the resin film described in [12] above. Multilayer printed wiring board.
[15] A polyphenylene ether derivative having an organic group substituted with an unsaturated aliphatic hydrocarbon group.
[16] The polyphenylene ether derivative according to the above [15], wherein the organic group substituted with the unsaturated aliphatic hydrocarbon group has a structure represented by the following general formula (a-1).
Figure JPOXMLDOC01-appb-C000010
(In the formula (a-1), R a1 is an unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms. M1 is 1 or 2, n1 is 0 or 1. * represents another structure. The binding position to is shown.)
[17] The polyphenylene ether derivative according to the above [15] or [16], wherein the organic group substituted with the unsaturated aliphatic hydrocarbon group has a structure represented by the following general formula (a-2).
Figure JPOXMLDOC01-appb-C000011
(In the formula (a-2), R a2 and R a3 are each independently an unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms. * Represents a bonding position to another structure.)
[18] The polyphenylene ether derivative according to any one of the above [15] to [17], wherein the total number of the unsaturated aliphatic hydrocarbon groups is 2 or more.
[19] The polyphenylene ether derivative according to any one of the above [15] to [18], wherein the total number of the unsaturated aliphatic hydrocarbon groups is 4 or more.
[20] The polyphenylene according to any one of the above [15] to [19], wherein the unsaturated aliphatic hydrocarbon group is a vinyl group, an isopropenyl group, an allyl group, a 1-methylallyl group or a 3-butenyl group. Ether derivative.
　本発明によれば、１０ＧＨｚ帯以上の高周波数帯において優れた誘電特性（低誘電率及び低誘電正接）を発現し得る樹脂組成物、該樹脂組成物の硬化物、プリプレグ、樹脂フィルム、多層プリント配線板及びミリ波レーダー用多層プリント配線板、並びに、そのような樹脂組成物を得ることが可能となるポリフェニレンエーテル誘導体を提供することができる。 According to the present invention, a resin composition capable of exhibiting excellent dielectric properties (low dielectric constant and low dielectric loss tangent) in a high frequency band of 10 GHz or higher, a cured product of the resin composition, a prepreg, a resin film, and a multilayer print. It is possible to provide a wiring board, a multilayer printed wiring board for millimeter-wave radar, and a polyphenylene ether derivative that makes it possible to obtain such a resin composition.
　本明細書中に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。また、数値範囲の下限値及び上限値は、それぞれ他の数値範囲の下限値又は上限値と任意に組み合わせられる。
　また、本明細書に例示する各成分及び材料は、特に断らない限り、１種類を単独で使用してもよいし、２種類以上を併用してもよい。本明細書において、組成物中の各成分の含有量は、組成物中に各成分に該当する物質が複数存在する場合、特に断らない限り、組成物中に存在する当該複数の物質の合計量を意味する。
　本明細書における記載事項を任意に組み合わせた態様も本発明に含まれる。 In the numerical ranges described in the present specification, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples. The lower limit value and the upper limit value of the numerical range are arbitrarily combined with the lower limit value and the upper limit value of the other numerical range.
Further, each component and material exemplified in the present specification may be used alone or in combination of two or more unless otherwise specified. In the present specification, the content of each component in the composition is the total amount of the plurality of substances present in the composition, unless a plurality of substances corresponding to each component are present in the composition. Means
The present invention also includes an embodiment in which the items described in this specification are arbitrarily combined.
［樹脂組成物］
　本発明の一態様は、
　（Ａ）不飽和脂肪族炭化水素基が置換した有機基を有するポリフェニレンエーテル誘導体［以下、単にポリフェニレンエーテル誘導体（Ａ）又は（Ａ）成分と略称することがある］、及び
　（Ｂ）Ｎ－置換マレイミド基を少なくとも２個有するマレイミド化合物及びその誘導体からなる群から選択される少なくとも１種類［以下、単にマレイミド化合物（Ｂ）又は（Ｂ）成分と略称することがある］、
を含有してなる樹脂組成物である。
　以下、各成分について順に詳述する。 [Resin composition]
One aspect of the present invention is
(A) Polyphenylene ether derivative having an organic group substituted with an unsaturated aliphatic hydrocarbon group [hereinafter, may be simply referred to as polyphenylene ether derivative (A) or component (A)], and (B) N-substituted At least one kind selected from the group consisting of a maleimide compound having at least two maleimide groups and a derivative thereof [hereinafter, sometimes simply referred to as maleimide compound (B) or (B) component],
It is a resin composition containing.
Hereinafter, each component will be described in detail in order.
＜ポリフェニレンエーテル誘導体（Ａ）＞
　ポリフェニレンエーテル誘導体（Ａ）は、不飽和脂肪族炭化水素基が置換した有機基を有しており、好ましくは、少なくとも一方の末端に不飽和脂肪族炭化水素基が置換した有機基を有する。本発明は、当該ポリフェニレンエーテル誘導体（Ａ）自体も提供する。このようなポリフェニレンエーテル誘導体（Ａ）を使用することによって、（Ｂ）成分が有するＮ－置換マレイミド基の炭素－炭素二重結合部位とのエン反応、場合によってはさらにディールス・アルダー反応が生じ得ることとなり、このことが、１０ＧＨｚ帯以上の高周波数帯における誘電特性の向上に起因しているのではないかと推察する。
　不飽和脂肪族炭化水素基が置換した有機基は、（Ａ）成分の片末端に有していてもよいし、両末端に有していてもよいし、中心骨格に有していてもよい。（Ａ）成分としては、片末端に不飽和脂肪族炭化水素基が置換した有機基を有するポリフェニレンエーテル誘導体、両末端に不飽和脂肪族炭化水素基が置換した有機基を有するポリフェニレンエーテル誘導体、及び中心骨格に不飽和脂肪族炭化水素基が置換した有機基を有するポリフェニレンエーテル誘導体からなる群から選択される２種以上の混合物であってもよい。（Ａ）成分としては、片末端に不飽和脂肪族炭化水素基が置換した有機基を有するポリフェニレンエーテル誘導体を含有することが好ましく、片末端に不飽和脂肪族炭化水素基が置換した有機基を有するポリフェニレンエーテル誘導体そのものであることがより好ましい。
　（Ａ）成分が、片末端に不飽和脂肪族炭化水素基が置換した有機基を有するポリフェニレンエーテル誘導体を含有する場合、（Ａ）成分中、片末端に不飽和脂肪族炭化水素基が置換した有機基を有するポリフェニレンエーテル誘導体の含有量は、３０質量％以上であってもよく、４５質量％以上であってもよく、５５質量％以上であってもよく、７０質量％以上であってもよく、９０質量％以上であってもよく、実質的に１００質量％であってもよい。 <Polyphenylene ether derivative (A)>
The polyphenylene ether derivative (A) has an organic group substituted with an unsaturated aliphatic hydrocarbon group, and preferably has an organic group substituted with an unsaturated aliphatic hydrocarbon group at least at one end. The present invention also provides the polyphenylene ether derivative (A) itself. By using such a polyphenylene ether derivative (A), an ene reaction with the carbon-carbon double bond site of the N-substituted maleimide group of the component (B), and in some cases, a Diels-Alder reaction can occur. Therefore, it is speculated that this may be due to the improvement of the dielectric characteristics in the high frequency band of 10 GHz or higher.
The organic group substituted with the unsaturated aliphatic hydrocarbon group may be present at one end of the component (A), may be present at both ends of the component (A), or may be present in the central skeleton. . As the component (A), a polyphenylene ether derivative having an organic group substituted with an unsaturated aliphatic hydrocarbon group at one end, a polyphenylene ether derivative having an organic group substituted with an unsaturated aliphatic hydrocarbon group at both ends, and It may be a mixture of two or more kinds selected from the group consisting of polyphenylene ether derivatives having an organic group substituted with an unsaturated aliphatic hydrocarbon group in the central skeleton. The component (A) preferably contains a polyphenylene ether derivative having an organic group substituted with an unsaturated aliphatic hydrocarbon group at one terminal, and an organic group substituted with an unsaturated aliphatic hydrocarbon group at one terminal More preferably, it is the polyphenylene ether derivative itself.
When the component (A) contains a polyphenylene ether derivative having an organic group substituted with an unsaturated aliphatic hydrocarbon group at one end, in the component (A), an unsaturated aliphatic hydrocarbon group was substituted at one end The content of the polyphenylene ether derivative having an organic group may be 30% by mass or more, 45% by mass or more, 55% by mass or more, and 70% by mass or more. It may be 90% by mass or more, or may be substantially 100% by mass.
　（Ａ）成分が有する前記「不飽和脂肪族炭化水素基が置換した有機基」における「不飽和脂肪族炭化水素基」としては、例えば、ビニル基、イソプロペニル基、アリル基、１－メチルアリル基、３－ブテニル基等が挙げられる。これらの中でも、１０ＧＨｚ帯以上の高周波数帯における誘電特性の観点から、炭素数２～１０の不飽和脂肪族炭化水素基が好ましく、炭素数２～５の不飽和脂肪族炭化水素基がより好ましく、アリル基がさらに好ましい。なお、本発明においては、マレイミド基及び（メタ）アクリロイル基等の様に、一部に不飽和脂肪族炭化水素基を有しているが、その基全体として見たときに不飽和脂肪族炭化水素基とは言えない基は、前記「不飽和脂肪族炭化水素基が置換した有機基」における「不飽和脂肪族炭化水素基」に含まれない。
　前記（Ａ）成分が有する不飽和脂肪族炭化水素基の合計数は、１０ＧＨｚ帯以上の高周波数帯における誘電特性の観点から、好ましくは２つ以上、より好ましくは４つ以上であり、上限値に特に制限はなく、８つ以下であってもよいし、６つ以下であってもよい。さらには、前記（Ａ）成分の片末端に有する不飽和脂肪族炭化水素基の合計数は、１０ＧＨｚ帯以上の高周波数帯における誘電特性の観点から、好ましくは２つ以上、より好ましくは４つ以上であり、上限値に特に制限はなく、８つ以下であってもよいし、６つ以下であってもよい。
　前記（Ａ）成分が有する不飽和脂肪族炭化水素基の合計数及び前記（Ａ）成分の片末端に有する不飽和脂肪族炭化水素基の合計数は、いずれも４つであることが最も好ましい。 Examples of the “unsaturated aliphatic hydrocarbon group” in the “organic group substituted with an unsaturated aliphatic hydrocarbon group” included in the component (A) include, for example, vinyl group, isopropenyl group, allyl group and 1-methylallyl group. , 3-butenyl group and the like. Among these, an unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms is preferable, and an unsaturated aliphatic hydrocarbon group having 2 to 5 carbon atoms is more preferable, from the viewpoint of dielectric properties in a high frequency band of 10 GHz band or higher. , And allyl groups are more preferred. Incidentally, in the present invention, such as a maleimide group and a (meth) acryloyl group, partially has an unsaturated aliphatic hydrocarbon group, but when viewed as a whole, the unsaturated aliphatic hydrocarbon group A group that cannot be said to be a hydrogen group is not included in the "unsaturated aliphatic hydrocarbon group" in the above "organic group substituted with an unsaturated aliphatic hydrocarbon group".
The total number of unsaturated aliphatic hydrocarbon groups contained in the component (A) is preferably 2 or more, more preferably 4 or more, from the viewpoint of dielectric properties in a high frequency band of 10 GHz band or more, and the upper limit value. Is not particularly limited, and may be 8 or less, or 6 or less. Further, the total number of unsaturated aliphatic hydrocarbon groups at one end of the component (A) is preferably 2 or more, more preferably 4 from the viewpoint of dielectric properties in a high frequency band of 10 GHz band or higher. As described above, the upper limit value is not particularly limited and may be 8 or less, or 6 or less.
Most preferably, the total number of unsaturated aliphatic hydrocarbon groups contained in the component (A) and the total number of unsaturated aliphatic hydrocarbon groups contained in one end of the component (A) are four. .
　前記「不飽和脂肪族炭化水素基が置換した有機基」としては、１０ＧＨｚ帯以上の高周波数帯における誘電特性の観点から、下記一般式（ａ－１）で表される構造を有することが好ましい。
Figure JPOXMLDOC01-appb-C000012
（式（ａ－１）中、Ｒａ１は炭素数２～１０の不飽和脂肪族炭化水素基である。ｍ１は１又は２であり、ｎ１は０又は１である。＊は、他の構造への結合位置を示す。） The “unsaturated aliphatic hydrocarbon group-substituted organic group” preferably has a structure represented by the following general formula (a-1) from the viewpoint of dielectric properties in a high frequency band of 10 GHz or higher. .
Figure JPOXMLDOC01-appb-C000012
(In the formula (a-1), R a1 is an unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms. M1 is 1 or 2, n1 is 0 or 1. * represents another structure. The binding position to is shown.)
　上記一般式（ａ－１）中、Ｒａ１が表す炭素数２～１０の不飽和脂肪族炭化水素基としては、例えば、ビニル基、イソプロペニル基、アリル基、１－メチルアリル基、３－ブテニル基等が挙げられる。これらの中でも、１０ＧＨｚ帯以上の高周波数帯における誘電特性の観点から、炭素数２～５の不飽和脂肪族炭化水素基が好ましく、アリル基がより好ましい。
　ｍ１は、１であってもよいし、２であってもよいが、１であることが好ましい。ｎ１は０であってもよいし、１であってもよい。
　なお、「不飽和脂肪族炭化水素基が置換した有機基」が上記一般式（ａ－１）で表される構造を有する場合、「不飽和脂肪族炭化水素基が置換した有機基」の少なくとも一部に上記一般式（ａ－１）で表される構造が含まれていればよい。 Examples of the unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms represented by R a1 in the above general formula (a-1) include a vinyl group, an isopropenyl group, an allyl group, a 1-methylallyl group, and 3-butenyl. Groups and the like. Among these, an unsaturated aliphatic hydrocarbon group having 2 to 5 carbon atoms is preferable, and an allyl group is more preferable, from the viewpoint of dielectric characteristics in a high frequency band of 10 GHz or higher.
m1 may be 1 or 2, but is preferably 1. n1 may be 0 or 1.
When the “organic group substituted with an unsaturated aliphatic hydrocarbon group” has a structure represented by the above general formula (a-1), at least the “organic group substituted with an unsaturated aliphatic hydrocarbon group” The structure represented by the general formula (a-1) may be included in part.
　また、前記「不飽和脂肪族炭化水素基が置換した有機基」としては、１０ＧＨｚ帯以上の高周波数帯における誘電特性及び相容性の観点から、下記一般式（ａ－２）で表される構造を有する態様も好ましい。
Figure JPOXMLDOC01-appb-C000013
（式（ａ－２）中、Ｒａ２及びＲａ３は、各々独立に、炭素数２～１０の不飽和脂肪族炭化水素基である。＊は、他の構造への結合位置を示す。） The "unsaturated aliphatic hydrocarbon group-substituted organic group" is represented by the following general formula (a-2) from the viewpoint of dielectric properties and compatibility in a high frequency band of 10 GHz or higher. An embodiment having a structure is also preferable.
Figure JPOXMLDOC01-appb-C000013
(In the formula (a-2), R a2 and R a3 are each independently an unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms. * Represents a bonding position to another structure.)
　上記一般式（ａ－２）中、Ｒａ２及びＲａ３が表す炭素数２～１０の不飽和脂肪族炭化水素基は、前記一般式（ａ－１）中のＲａ１と同じものが挙げられ、同じものが好ましい。
　なお、「不飽和脂肪族炭化水素基が置換した有機基」が上記一般式（ａ－２）で表される構造を有する場合、「不飽和脂肪族炭化水素基が置換した有機基」の少なくとも一部に上記一般式（ａ－２）で表される構造が含まれていればよい。 Examples of the unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms represented by R a2 and R a3 in the general formula (a-2) include the same ones as R a1 in the general formula (a-1). , The same is preferable.
When the “organic group substituted with an unsaturated aliphatic hydrocarbon group” has a structure represented by the above general formula (a-2), at least the “organic group substituted with an unsaturated aliphatic hydrocarbon group” The structure represented by the general formula (a-2) may be included in part.
　前記「不飽和脂肪族炭化水素基が置換した有機基」としては、１０ＧＨｚ帯以上の高周波数帯における誘電特性の観点から、下記一般式（ａ－３）～（ａ－５）のいずれかで表される構造であることがより好ましく、１０ＧＨｚ帯以上の高周波数帯における誘電特性及び相容性の観点から、下記一般式（ａ－５）で表される構造であることがさらに好ましい。 The “organic group substituted with an unsaturated aliphatic hydrocarbon group” is one of the following general formulas (a-3) to (a-5) from the viewpoint of dielectric properties in a high frequency band of 10 GHz or higher. The structure represented by the following general formula (a-5) is more preferable from the viewpoint of dielectric properties and compatibility in a high frequency band of 10 GHz or higher.
Figure JPOXMLDOC01-appb-C000014
（式（ａ－３）中、Ｒａ４は炭素数２～１０の不飽和脂肪族炭化水素基である。＊は、他の構造への結合位置を示す。）
Figure JPOXMLDOC01-appb-C000014
(In the formula (a-3), R a4 is an unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms. * Represents a bonding position to another structure.)
Figure JPOXMLDOC01-appb-C000015
（式（ａ－４）中、Ｒａ５及びＲａ６は、各々独立に、炭素数２～１０の不飽和脂肪族炭化水素基である。Ｘａ１は、炭素数１～６の脂肪族炭化水素基である。＊は、他の構造への結合位置を示す。）
Figure JPOXMLDOC01-appb-C000015
(In the formula (a-4), R a5 and R a6 are each independently an unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms. X a1 is an aliphatic hydrocarbon group having 1 to 6 carbon atoms. It is a group. * Indicates a bonding position to another structure.)
Figure JPOXMLDOC01-appb-C000016
（式（ａ－５）中、Ｒａ７～Ｒａ１０は、各々独立に、炭素数２～１０の不飽和脂肪族炭化水素基である。Ｘａ２は有機基である。＊は、他の構造への結合位置を示す。）
Figure JPOXMLDOC01-appb-C000016
(In the formula (a-5), R a7 to R a10 are each independently an unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms. X a2 is an organic group. * Is another structure. The binding position to is shown.)
　上記一般式（ａ－３）～（ａ－５）中のＲａ４～Ｒａ１０が表す炭素数２～１０の不飽和脂肪族炭化水素基としては、一般式（ａ－１）中のＲａ１の場合と同じものが挙げられ、好ましいものも同じである。
　上記一般式（ａ－４）中のＸａ１が表す炭素数１～６の脂肪族炭化水素基としては、例えば、メチレン基、エチレン基、トリメチレン基等の炭素数１～６のアルキレン基；イソプロピリデン基等の炭素数２～６のアルキリデン基が挙げられる。これらの中でも、メチレン基、イソプロピリデン基が好ましく、イソプロピリデン基がより好ましい。
　上記一般式（ａ－５）中のＸａ２が表す有機基としては、一部にヘテロ原子を含有していてもよい脂肪族炭化水素基、一部にヘテロ原子を含有していてもよい脂環式炭化水素基、一部にヘテロ原子を含有していてもよい芳香族炭化水素基、並びにこれらの任意の組み合わせからなる基等が挙げられる。前記ヘテロ原子としては、酸素原子、窒素原子、硫黄原子等が挙げられる。Ｘａ２が表す有機基としては、１０ＧＨｚ帯以上の高周波数帯における誘電特性の観点から、ヘテロ原子を含有していない基であることが好ましく、ヘテロ原子を含有していない脂肪族炭化水素基、ヘテロ原子を含有していない脂環式炭化水素基がより好ましく、ヘテロ原子を含有していない脂肪族炭化水素基とヘテロ原子を含有していない脂環式炭化水素基との組み合わせからなる基であることがさらに好ましい。 Examples of the unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms represented by R a4 to R a10 in the general formulas (a-3) to (a-5) include R a1 in the general formula (a-1). The same thing as the case of is mentioned, and a preferable thing is also the same.
Examples of the aliphatic hydrocarbon group having 1 to 6 carbon atoms represented by X a1 in the general formula (a-4) include alkylene groups having 1 to 6 carbon atoms such as methylene group, ethylene group and trimethylene group; Examples thereof include an alkylidene group having 2 to 6 carbon atoms such as a lidene group. Among these, a methylene group and an isopropylidene group are preferable, and an isopropylidene group is more preferable.
The organic group represented by X a2 in the general formula (a-5) is an aliphatic hydrocarbon group which may partially contain a hetero atom, or an aliphatic hydrocarbon group which may partially contain a hetero atom. Examples thereof include a cyclic hydrocarbon group, an aromatic hydrocarbon group which may partially contain a hetero atom, and a group composed of any combination thereof. Examples of the hetero atom include an oxygen atom, a nitrogen atom and a sulfur atom. The organic group represented by X a2 is preferably a group containing no hetero atom from the viewpoint of dielectric properties in a high frequency band of 10 GHz or higher, and an aliphatic hydrocarbon group containing no hetero atom, An alicyclic hydrocarbon group containing no heteroatoms is more preferable, and it is a group consisting of a combination of an aliphatic hydrocarbon group containing no heteroatoms and an alicyclic hydrocarbon group containing no heteroatoms. It is more preferable that there is.
　上記一般式（ａ－３）、（ａ－４）又は（ａ－５）で表される構造について、より好ましい態様は、１０ＧＨｚ帯以上の高周波数帯における誘電特性の観点から、それぞれ下記式（ａ－３’）、（ａ－４’）又は（ａ－５’）で表される構造である。これらの中でも、１０ＧＨｚ帯以上の高周波数帯における誘電特性及び相容性の観点から、下記式（ａ－４’）又は（ａ－５’）で表される構造がより好ましく、下記式（ａ－５’）で表される構造がさらに好ましい。
Figure JPOXMLDOC01-appb-C000017
（上記式中、Ｘａ２は前記一般式（ａ－５）中のＸａ２と同じである。＊は、他の構造への結合位置を示す。） With respect to the structure represented by the above general formula (a-3), (a-4) or (a-5), more preferable embodiments are the following formulas from the viewpoint of the dielectric properties in the high frequency band of 10 GHz band or higher. a-3 ′), (a-4 ′) or (a-5 ′). Among these, the structure represented by the following formula (a-4 ′) or (a-5 ′) is more preferable from the viewpoint of dielectric properties and compatibility in a high frequency band of 10 GHz or higher, and the following formula (a The structure represented by -5 ') is more preferable.
Figure JPOXMLDOC01-appb-C000017
(In the above formula, X a2 is the same as X a2 in the above general formula (a-5). * Represents a bonding position to another structure.)
　（Ａ）成分は、ポリフェニレンエーテル誘導体であるため、いうまでもなく、下記一般式（Ｉ）で表される構造単位も有する。
Figure JPOXMLDOC01-appb-C000018
（式中、Ｒａ１１は、各々独立に、炭素数１～５の脂肪族炭化水素基又はハロゲン原子である。ｐ１は０～４の整数である。） Since the component (A) is a polyphenylene ether derivative, it goes without saying that it also has a structural unit represented by the following general formula (I).
Figure JPOXMLDOC01-appb-C000018
(In the formula, R a11 is each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. P1 is an integer of 0 to 4.)
　前記一般式（Ｉ）中のＲａ１１は、各々独立に、炭素数１～５の脂肪族炭化水素基又はハロゲン原子である。該脂肪族炭化水素基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔ－ブチル基、ｎ－ペンチル基等が挙げられる。該脂肪族炭化水素基としては、炭素数１～３の脂肪族炭化水素基が好ましく、メチル基がより好ましい。また、ハロゲン原子としては、例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられる。
　以上の中でも、Ｒａ１１としては、好ましくは炭素数１～５の脂肪族炭化水素基である。
　ｐ１は０～４の整数であり、０～２の整数であってもよく、２であってもよい。なお、ｐ１が１又は２である場合、Ｒａ１１はベンゼン環上のオルト位（但し、酸素原子の置換位置を基準とする。）に置換していてもよい。また、ｐ１が２以上である場合、複数のＲａ１１同士は、それぞれ同一であっても異なっていてもよい。
　前記一般式（Ｉ）で表される構造単位としては、具体的には、下記一般式（Ｉ'）で表される構造単位であってもよい。
Figure JPOXMLDOC01-appb-C000019
 R a11 in the general formula (I) is each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. Examples of the aliphatic hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group and the like. As the aliphatic hydrocarbon group, an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferable, and a methyl group is more preferable. Moreover, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Among the above, R a11 is preferably an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
p1 is an integer of 0 to 4, and may be an integer of 0 to 2 or 2. In addition, when p1 is 1 or 2, R a11 may be substituted at the ortho position on the benzene ring (however, based on the substitution position of the oxygen atom). Further, when p1 is 2 or more, the plurality of R a11 's may be the same or different.
The structural unit represented by the general formula (I) may be specifically a structural unit represented by the following general formula (I ′).
Figure JPOXMLDOC01-appb-C000019
　ポリフェニレンエーテル誘導体（Ａ）は、下記一般式（Ａ－ｉ）～（Ａ－iii）のいずれかで表されるポリフェニレンエーテル誘導体を含有していてもよく、特に下記一般式（Ａ－ii）又は（Ａ－iii）で表されるポリフェニレンエーテル誘導体を含有していることが好ましく、下記一般式（Ａ－iii）で表されるポリフェニレンエーテル誘導体を含有していることがより好ましい。
Figure JPOXMLDOC01-appb-C000020
（上記式中、Ｘａ２は前記一般式（ａ－５）中のＸａ２と同じである。ｑ１～ｑ３は、各々独立に、１～２００の整数である。） The polyphenylene ether derivative (A) may contain a polyphenylene ether derivative represented by any of the following general formulas (Ai) to (A-iii), and in particular, the following general formula (A-ii) or It preferably contains a polyphenylene ether derivative represented by (A-iii), and more preferably contains a polyphenylene ether derivative represented by the following general formula (A-iii).
Figure JPOXMLDOC01-appb-C000020
(In the formula, X a2 is the formula (a-5) X a2 to be the same .q1 ~ q3 in are each independently an integer of 1 to 200.)
　前記一般式（Ａ－ｉ）～（Ａ－iii）において、ｑ１～ｑ３は各々独立に、１～２００の整数であり、１０ＧＨｚ帯以上の高周波数帯における誘電特性の観点及び樹脂組成物の相容性の観点から、好ましくは１～１５０の整数、より好ましくは１～１２０の整数、さらに好ましくは１～１００の整数である。ｑ１～ｑ３の前記数値範囲の下限値としては、１０以上であってもよく、２０以上であってもよく、２５以上であってもよい。
　前記一般式（Ａ－ｉ）～（Ａ－iii）のいずれにおいても、ｑ１～ｑ３の値が異なるポリフェニレンエーテル誘導体の混合物であってもよく、通常、混合物となる傾向にある。 In the general formulas (Ai) to (A-iii), q1 to q3 are each independently an integer of 1 to 200, and the phase of the resin composition and the viewpoint of dielectric properties in a high frequency band of 10 GHz band or higher. From the viewpoint of compatibility, it is preferably an integer of 1 to 150, more preferably an integer of 1 to 120, still more preferably an integer of 1 to 100. The lower limit value of the numerical range of q1 to q3 may be 10 or more, 20 or more, or 25 or more.
In any of the above general formulas (Ai) to (A-iii), a mixture of polyphenylene ether derivatives having different values of q1 to q3 may be used, and usually tends to be a mixture.
（数平均分子量（Ｍｎ））
　ポリフェニレンエーテル誘導体（Ａ）の数平均分子量としては、好ましくは１，０００～２５，０００である。ポリフェニレンエーテル誘導体（Ａ）の数平均分子量が１，０００以上であれば、１０ＧＨｚ帯以上の高周波数帯における誘電特性がより一層良好となる傾向にある。また、ポリフェニレンエーテル誘導体（Ａ）の数平均分子量が２５，０００以下であれば、樹脂組成物の相容性が良好となり、長期間放置しておいても分離し難くなる傾向にある。同様の観点から、ポリフェニレンエーテル誘導体（Ａ）の数平均分子量は、より好ましくは２，０００～２０，０００、さらに好ましくは２，５００～１５，０００、よりさらに好ましくは３，０００～１０，０００、特に好ましくは３，０００～７，５００、最も好ましくは３，０００～６，０００である。
　なお、本明細書において、数平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により、標準ポリスチレンを用いた検量線から換算した値であり、より詳細には実施例に記載の数平均分子量の測定方法により求めた値である。 (Number average molecular weight (Mn))
The number average molecular weight of the polyphenylene ether derivative (A) is preferably 1,000 to 25,000. When the number average molecular weight of the polyphenylene ether derivative (A) is 1,000 or more, the dielectric property in the high frequency band of 10 GHz band or more tends to be further improved. Further, when the number average molecular weight of the polyphenylene ether derivative (A) is 25,000 or less, the compatibility of the resin composition becomes good, and it tends to be difficult to separate even if left for a long time. From the same viewpoint, the number average molecular weight of the polyphenylene ether derivative (A) is more preferably 2,000 to 20,000, further preferably 2,500 to 15,000, still more preferably 3,000 to 10,000. , Particularly preferably 3,000 to 7,500, most preferably 3,000 to 6,000.
In the present specification, the number average molecular weight is a value converted from a calibration curve using standard polystyrene by gel permeation chromatography (GPC), and more specifically, measurement of the number average molecular weight described in Examples. It is the value obtained by the method.
（ポリフェニレンエーテル誘導体（Ａ）の製造方法）
　以下、ポリフェニレンエーテル誘導体（Ａ）の製造方法の一態様について説明するが、特に下記説明に限定されるものではない。
　例えば、前記一般式（ａ－１）～（ａ－５）のいずれかで表される構造を有するフェノール化合物［以下、不飽和脂肪族炭化水素基含有フェノール化合物（１）と称する］と、数平均分子量１０，０００～３０，０００のポリフェニレンエーテル［以下、原料ポリフェニレンエーテルと称することがある］を有機溶媒中で、再分配反応をさせることによりポリフェニレンエーテルの低分子量化を伴いながら、ポリフェニレンエーテル誘導体（Ａ）を製造することができる。 (Method for producing polyphenylene ether derivative (A))
Hereinafter, one embodiment of the method for producing the polyphenylene ether derivative (A) will be described, but the invention is not particularly limited to the following description.
For example, a phenol compound having a structure represented by any one of the above general formulas (a-1) to (a-5) [hereinafter referred to as unsaturated aliphatic hydrocarbon group-containing phenol compound (1)] A polyphenylene ether derivative having an average molecular weight of 10,000 to 30,000 [hereinafter, sometimes referred to as a raw material polyphenylene ether] is redistributed in an organic solvent to reduce the molecular weight of the polyphenylene ether. (A) can be produced.
　なお、前記再分配反応は、例えば、既に重合して製造された原料ポリフェニレンエーテルに対して不飽和脂肪族炭化水素基含有フェノール化合物（１）を混合し、必要に応じて後述の反応触媒を添加することによって、不飽和脂肪族炭化水素基含有フェノール化合物（１）のオキシラジカルが、原料ポリフェニレンエーテル中の酸素原子が結合している炭素原子へ攻撃してそこでＯ－Ｃ結合が切れて低分子量化する反応である。その際、攻撃した不飽和脂肪族炭化水素基含有フェノール化合物（１）のオキシラジカルが、結合が切れた炭素原子と結合し、ポリフェニレンエーテルの構造に取り込まれる。該再分配反応としては、公知の方法を利用及び応用することができる。 In the redistribution reaction, for example, a raw material polyphenylene ether produced by polymerization is mixed with an unsaturated aliphatic hydrocarbon group-containing phenol compound (1), and a reaction catalyst described later is added if necessary. By doing so, the oxy radical of the unsaturated aliphatic hydrocarbon group-containing phenol compound (1) attacks the carbon atom to which the oxygen atom in the raw material polyphenylene ether is bonded, and the OC bond is broken there, resulting in a low molecular weight. It is a reaction that changes. At that time, the attacked oxy radical of the unsaturated aliphatic hydrocarbon group-containing phenol compound (1) is bonded to the carbon atom whose bond has been broken, and is incorporated into the structure of the polyphenylene ether. A known method can be used and applied as the redistribution reaction.
　ポリフェニレンエーテル誘導体（Ａ）の分子量は、不飽和脂肪族炭化水素基含有フェノール化合物（１）の使用量によって制御することができ、不飽和脂肪族炭化水素基含有フェノール化合物（１）の使用量が多いほどポリフェニレンエーテル誘導体（Ａ）は低分子量化される。つまり、最終的に製造されるポリフェニレンエーテル誘導体（Ａ）の数平均分子量が好適な範囲となるように不飽和脂肪族炭化水素基含有フェノール化合物（１）の使用量を適宜調整すればよい。
　不飽和脂肪族炭化水素基含有フェノール化合物（１）の使用量としては、特に制限されるものではないが、例えば、不飽和脂肪族炭化水素基含有フェノール化合物（１）と反応させる原料ポリフェニレンエーテルの数平均分子量が１０，０００～３０，０００である場合、該原料ポリフェニレンエーテル１モルに対する不飽和脂肪族炭化水素基含有フェノール化合物（１）の水酸基が１～１０モルとなる量で使用することにより、数平均分子量が前記した好ましい範囲内のポリフェニレンエーテル誘導体（Ａ）が得られる。 The molecular weight of the polyphenylene ether derivative (A) can be controlled by the amount of the unsaturated aliphatic hydrocarbon group-containing phenol compound (1) used, and the amount of the unsaturated aliphatic hydrocarbon group-containing phenol compound (1) used is The higher the amount, the lower the molecular weight of the polyphenylene ether derivative (A). That is, the amount of the unsaturated aliphatic hydrocarbon group-containing phenol compound (1) used may be appropriately adjusted so that the number average molecular weight of the finally produced polyphenylene ether derivative (A) falls within a suitable range.
The amount of the unsaturated aliphatic hydrocarbon group-containing phenol compound (1) to be used is not particularly limited, but for example, the amount of the raw material polyphenylene ether to be reacted with the unsaturated aliphatic hydrocarbon group-containing phenol compound (1) When the number average molecular weight is 10,000 to 30,000, the unsaturated aliphatic hydrocarbon group-containing phenol compound (1) is used in an amount of 1 to 10 mol per 1 mol of the raw material polyphenylene ether. The polyphenylene ether derivative (A) having a number average molecular weight within the above-mentioned preferable range can be obtained.
　ポリフェニレンエーテル誘導体（Ａ）の製造工程で使用される有機溶媒は特に制限はないが、例えば、メタノール、エタノール、ブタノール、ブチルセロソルブ、エチレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテル等のアルコール；アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン；トルエン、キシレン、メシチレン等の芳香族炭化水素；メトキシエチルアセテート、エトキシエチルアセテート、ブトキシエチルアセテート、酢酸エチル等のエステル；Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチル－２－ピロリドン等の含窒素化合物などが挙げられる。これらは１種類を単独で用いてもよく、２種類以上を併用してもよい。これらの中でも、溶解性の観点から、トルエン、キシレン、メシチレンを選択してもよく、トルエンを選択することが好ましい。 The organic solvent used in the production process of the polyphenylene ether derivative (A) is not particularly limited, but examples thereof include alcohols such as methanol, ethanol, butanol, butyl cellosolve, ethylene glycol monomethyl ether, propylene glycol monomethyl ether; acetone, methyl ethyl ketone, methyl. Ketones such as isobutyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and mesitylene; esters such as methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate, ethyl acetate; N, N-dimethylformamide, N, N-dimethyl Examples thereof include nitrogen-containing compounds such as acetamide and N-methyl-2-pyrrolidone. These may be used alone or in combination of two or more. Among these, toluene, xylene, and mesitylene may be selected from the viewpoint of solubility, and it is preferable to select toluene.
　また、ポリフェニレンエーテル誘導体（Ａ）の製造工程においては、前述のとおり、必要に応じて反応触媒を使用することができる。この反応触媒としては、例えば、再現性良く安定した数平均分子量のポリフェニレンエーテル誘導体（Ａ）を得るという観点から、ｔ－ブチルペルオキシイソプロピルモノカーボネート等の有機過酸化物とナフテン酸マンガン等のカルボン酸金属塩とを併用することが好ましい。また、反応触媒の使用量は特に制限はない。ポリフェニレンエーテル誘導体（Ａ）を製造する際の反応速度及びゲル化抑制の観点から、例えば、不飽和脂肪族炭化水素基含有フェノール化合物（１）と反応させる原料ポリフェニレンエーテル１００質量部に対して、有機過酸化物を０．５～５質量部、カルボン酸金属塩を０．０５～０．５質量部としてもよい。 Further, in the production process of the polyphenylene ether derivative (A), a reaction catalyst can be used as necessary as described above. Examples of the reaction catalyst include, for example, an organic peroxide such as t-butylperoxyisopropyl monocarbonate and a carboxylic acid such as manganese naphthenate from the viewpoint of obtaining a polyphenylene ether derivative (A) having a stable and reproducible number average molecular weight. It is preferable to use together with a metal salt. The amount of the reaction catalyst used is not particularly limited. From the viewpoint of reaction rate when producing the polyphenylene ether derivative (A) and suppression of gelation, for example, with respect to 100 parts by mass of the raw material polyphenylene ether to be reacted with the unsaturated aliphatic hydrocarbon group-containing phenol compound (1), organic The peroxide may be 0.5 to 5 parts by mass and the carboxylic acid metal salt may be 0.05 to 0.5 parts by mass.
　前記不飽和脂肪族炭化水素基含有フェノール化合物（１）、前記数平均分子量１０，０００～３０，０００の原料ポリフェニレンエーテル、有機溶媒及び必要により反応触媒を反応器に所定量仕込み、加熱、保温、撹拌しながら反応させることによりポリフェニレンエーテル誘導体（Ａ）が得られる。この工程での反応温度及び反応時間は、公知の再分配反応時における反応条件を適用でき、適宜調整すればよい。
　作業性及びゲル化抑制の観点から、並びに前記所望の数平均分子量の（Ａ）成分を得る観点から、例えば、反応温度７０～１１０℃、反応時間１～８時間で反応を行ってもよい。 The unsaturated aliphatic hydrocarbon group-containing phenol compound (1), the raw material polyphenylene ether having the number average molecular weight of 10,000 to 30,000, an organic solvent and, if necessary, a reaction catalyst are charged in a predetermined amount in a reactor, and heated and kept warm. The polyphenylene ether derivative (A) is obtained by reacting with stirring. The reaction temperature and reaction time in this step can be appropriately adjusted according to known reaction conditions during redistribution reaction.
From the viewpoint of workability and suppression of gelation, and from the viewpoint of obtaining the component (A) having the desired number average molecular weight, the reaction may be carried out, for example, at a reaction temperature of 70 to 110 ° C. and a reaction time of 1 to 8 hours.
　前記ポリフェニレンエーテル誘導体（Ａ）の製造工程における反応中の固形分濃度（以下、反応濃度と称する）は、特に制限されるものではないが、例えば、１０～６０質量％であってもよく、２５～５５質量％であってもよい。反応濃度が１０質量％以上の場合、反応速度が遅くなりすぎず、製造コストの面でより有利な傾向にある。また、反応温度が６０質量％以下の場合、より良好な溶解性が得られる傾向にあり、さらに、溶液粘度が低くて撹拌効率がよく、ゲル化し難い傾向にある。 The solid content concentration (hereinafter referred to as reaction concentration) during the reaction in the production process of the polyphenylene ether derivative (A) is not particularly limited, but may be, for example, 10 to 60% by mass, 25 It may be up to 55 mass%. When the reaction concentration is 10% by mass or more, the reaction rate does not become too slow, and the production cost tends to be more advantageous. Further, when the reaction temperature is 60% by mass or less, better solubility tends to be obtained, and further, the solution viscosity is low, stirring efficiency is good, and gelation tends to be difficult.
　以上の様にして製造されたポリフェニレンエーテル誘導体（Ａ）の溶液は、後述のように必要に応じて濃縮して有機溶媒の一部を除去してもよいし、有機溶媒を追加して希釈してもよい。 The solution of the polyphenylene ether derivative (A) produced as described above may be concentrated as necessary to remove a part of the organic solvent as described below, or may be diluted by adding an organic solvent. May be.
　本発明の樹脂組成物は、当該（Ａ）成分の代わりに前記原料ポリフェニレンエーテルを含有させた樹脂組成物よりも、１０ＧＨｚ帯以上の高周波数帯における誘電特性が優れる傾向にある。 The resin composition of the present invention tends to have better dielectric properties in a high frequency band of 10 GHz or higher than a resin composition containing the raw material polyphenylene ether instead of the component (A).
＜マレイミド化合物（Ｂ）＞
　マレイミド化合物（Ｂ）は、Ｎ－置換マレイミド基を少なくとも２個有するマレイミド化合物及びその誘導体からなる群から選択される少なくとも１種である。該マレイミド化合物（Ｂ）は、前記ポリフェニレンエーテル誘導体（Ａ）を包含しない。さらに、マレイミド化合物（Ｂ）は、前記一般式（Ｉ）で表される構造単位を含有しないこと、換言すると、ポリフェニレンエーテル骨格を含有しないことが好ましい。
　また、前記「その誘導体」としては、前記Ｎ－置換マレイミド基を少なくとも２個有するマレイミド化合物と、後述するジアミン化合物（ｂ２）等のアミン化合物との付加反応物などが挙げられる。
　マレイミド化合物（Ｂ）としては、有機溶媒への溶解性、相容性、導体との接着性、及び１０ＧＨｚ帯以上の高周波数帯における誘電特性の観点から、Ｎ－置換マレイミド基を少なくとも２個有するマレイミド化合物の誘導体が好ましく、Ｎ－置換マレイミド基を少なくとも２個有するマレイミド化合物（ｂ１）［以下、単にマレイミド化合物（ｂ１）又は（ｂ１）成分と称することがある。］由来の構造単位とジアミン化合物（ｂ２）由来の構造単位とを有するポリアミノビスマレイミド化合物（以下、ポリアミノビスマレイミド化合物（Ｂ１）と称することがある）であることがより好ましい。
　なお、（ｂ１）成分由来の構造単位及び（ｂ２）成分由来の構造単位は、各々について、１種類であってもよく、２種類以上の組み合わせであってもよい。 <Maleimide compound (B)>
The maleimide compound (B) is at least one selected from the group consisting of maleimide compounds having at least two N-substituted maleimide groups and derivatives thereof. The maleimide compound (B) does not include the polyphenylene ether derivative (A). Furthermore, it is preferable that the maleimide compound (B) does not contain the structural unit represented by the general formula (I), in other words, does not contain the polyphenylene ether skeleton.
Examples of the “derivative thereof” include addition reaction products of the maleimide compound having at least two N-substituted maleimide groups and an amine compound such as a diamine compound (b2) described later.
The maleimide compound (B) has at least two N-substituted maleimide groups from the viewpoints of solubility in an organic solvent, compatibility, adhesion with a conductor, and dielectric properties in a high frequency band of 10 GHz or higher. A maleimide compound derivative is preferable, and a maleimide compound (b1) having at least two N-substituted maleimide groups [hereinafter, may be simply referred to as maleimide compound (b1) or (b1) component). ] It is more preferable that it is a polyamino bismaleimide compound (henceforth a polyamino bismaleimide compound (B1)) which has the structural unit derived from and the structural unit derived from the diamine compound (b2).
The structural unit derived from the component (b1) and the structural unit derived from the component (b2) may be of one type or a combination of two or more types.
　（ｂ１）成分の具体例としては、Ｎ－置換マレイミド基を２個以上有するマレイミド化合物であれば特に限定されないが、例えば、ビス（４－マレイミドフェニル）メタン、ポリフェニルメタンマレイミド、ビス（４－マレイミドフェニル）エーテル、ビス（４－マレイミドフェニル）スルホン、３，３’－ジメチル－５，５’－ジエチル－４，４’－ジフェニルメタンビスマレイミド、４－メチル－１，３－フェニレンビスマレイミド、ｍ－フェニレンビスマレイミド、２，２－ビス［４－（４－マレイミドフェノキシ）フェニル］プロパン等の芳香族マレイミド化合物；１，６－ビスマレイミド－（２，２，４－トリメチル）ヘキサン、ピロリロン酸バインダ型長鎖アルキルビスマレイミド等の脂肪族マレイミド化合物などが挙げられる。これらの中でも、導体との接着性及び機械特性の観点から、芳香族マレイミド化合物が好ましく、２，２－ビス［４－（４－マレイミドフェノキシ）フェニル］プロパン、３，３’－ジメチル－５，５’－ジエチル－４，４’－ジフェニルメタンビスマレイミドがより好ましい。 Specific examples of the component (b1) are not particularly limited as long as they are maleimide compounds having two or more N-substituted maleimide groups, and examples thereof include bis (4-maleimidophenyl) methane, polyphenylmethanemaleimide, bis (4- Maleimidophenyl) ether, bis (4-maleimidophenyl) sulfone, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide, 4-methyl-1,3-phenylenebismaleimide, m -Aromatic maleimide compounds such as phenylene bismaleimide, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane; 1,6-bismaleimide- (2,2,4-trimethyl) hexane, pyrrolilonic acid binder Examples include aliphatic maleimide compounds such as long-chain alkyl bismaleimide. . Among these, aromatic maleimide compounds are preferable from the viewpoint of adhesiveness to conductors and mechanical properties, and 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, 3,3′-dimethyl-5, More preferred is 5'-diethyl-4,4'-diphenylmethane bismaleimide.
　成分（ｂ１）由来の構造単位としては、下記一般式（Ｂ－１）で表される基及び下記一般式（Ｂ－２）で表される基からなる群から選択される少なくとも１種類が挙げられる。
Figure JPOXMLDOC01-appb-C000021
（式中、ＸＢ１は有機基を示し、＊は他の構造への結合位置を示す。） Examples of the structural unit derived from the component (b1) include at least one selected from the group consisting of a group represented by the following general formula (B-1) and a group represented by the following general formula (B-2). Be done.
Figure JPOXMLDOC01-appb-C000021
(In the formula, X B1 represents an organic group, and * represents a bonding position to another structure.)
　前記一般式（Ｂ－１）及び（Ｂ－２）中のＸＢ１は有機基であり、（ｂ１）成分の残基に相当する。なお、（ｂ１）成分の残基とは、（ｂ１）成分から結合に供された官能基、つまりマレイミド基を除いた部分の構造をいう。
　ＸＢ１が表す有機基としては、例えば、下記一般式（II）、（III）、（IV）又は（Ｖ）で表される基が挙げられる。 X B1 in the general formulas (B-1) and (B-2) is an organic group and corresponds to the residue of the component (b1). In addition, the residue of the component (b1) refers to the structure of the part excluding the functional group used for the bond, that is, the maleimide group, from the component (b1).
Examples of the organic group represented by X B1 include groups represented by general formulas (II), (III), (IV) or (V) shown below.
Figure JPOXMLDOC01-appb-C000022
（式中、Ｒｂ１は各々独立に、炭素数１～５の脂肪族炭化水素基又はハロゲン原子である。ｐは０～４の整数である。）
　Ｒｂ１が表す炭素数１～５の脂肪族炭化水素基、ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられる。
　ｐは０～４の整数であり、入手容易性の観点から、０～２の整数であってもよく、０又は１であってもよく、０であってもよい。ｐが２以上の整数である場合、複数のＲｂ１同士は同一であっても異なっていてもよい。
Figure JPOXMLDOC01-appb-C000022
(In the formula, each of R b1 is independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. P is an integer of 0 to 4.)
Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R b1 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
p is an integer of 0 to 4, and from the viewpoint of easy availability, it may be an integer of 0 to 2, 0 or 1, or 0. When p is an integer of 2 or more, a plurality of R b1 's may be the same or different.
Figure JPOXMLDOC01-appb-C000023
（式中、Ｒｂ２及びＲｂ３は各々独立に、炭素数１～５の脂肪族炭化水素基又はハロゲン原子である。Ｗ２は炭素数１～５のアルキレン基、炭素数２～５のアルキリデン基、エーテル基、スルフィド基、スルホニル基、カルボニルオキシ基、ケト基、単結合、又は下記一般式（III－１）で表される基である。ｑ及びｒは各々独立に０～４の整数である。）
　Ｒｂ２及びＲｂ３が表す炭素数１～５の脂肪族炭化水素基、ハロゲン原子としては、Ｒｂ１の場合と同じものが挙げられる。該脂肪族炭化水素基としては、炭素数１～３の脂肪族炭化水素基であってもよく、メチル基、エチル基であってもよく、エチル基であってもよい。
　Ｗ２が表す炭素数１～５のアルキレン基としては、例えば、メチレン基、１,２－ジメチレン基、１,３－トリメチレン基、１,４－テトラメチレン基、１,５－ペンタメチレン基等が挙げられる。該アルキレン基としては、高周波特性（低誘電率、低誘電正接）、導体との接着性、耐熱性、ガラス転移温度、熱膨張係数及び難燃性の観点から、炭素数１～３のアルキレン基であってもよく、メチレン基であってもよい。
　Ｗ２が表す炭素数２～５のアルキリデン基としては、例えば、エチリデン基、プロピリデン基、イソプロピリデン基、ブチリデン基、イソブチリデン基、ペンチリデン基、イソペンチリデン基等が挙げられる。これらの中でも、高周波特性（低誘電率、低誘電正接）、導体との接着性、耐熱性、ガラス転移温度、熱膨張係数及び難燃性の観点から、イソプロピリデン基であってもよい。
　Ｗ２としては、上記選択肢の中でも、炭素数１～５のアルキレン基、炭素数２～５のアルキリデン基であってもよい。
　ｑ及びｒは各々独立に０～４の整数であり、入手容易性の観点から、いずれも、０～２の整数であってもよく、０又は２であってもよい。ｑ又はｒが２以上の整数である場合、複数のＲｂ２同士又はＲｂ３同士は、それぞれ同一であっても異なっていてもよい。
　なお、Ｗ２が表す一般式（III－１）で表される基は以下のとおりである。
Figure JPOXMLDOC01-appb-C000023
(In the formula, R b2 and R b3 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. W 2 is an alkylene group having 1 to 5 carbon atoms, an alkylidene having 2 to 5 carbon atoms. A group, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, a single bond, or a group represented by the following general formula (III-1), wherein q and r are each independently an integer of 0 to 4. It is.)
As the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R b2 and R b3 , the same ones as in the case of R b1 can be mentioned. The aliphatic hydrocarbon group may be an aliphatic hydrocarbon group having 1 to 3 carbon atoms, a methyl group, an ethyl group, or an ethyl group.
Examples of the alkylene group having 1 to 5 carbon atoms represented by W 2 include methylene group, 1,2-dimethylene group, 1,3-trimethylene group, 1,4-tetramethylene group, and 1,5-pentamethylene group. Is mentioned. The alkylene group is an alkylene group having 1 to 3 carbon atoms from the viewpoints of high-frequency characteristics (low dielectric constant, low dielectric loss tangent), adhesion with conductors, heat resistance, glass transition temperature, thermal expansion coefficient and flame retardancy. Or may be a methylene group.
Examples of the alkylidene group having 2 to 5 carbon atoms represented by W 2 include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group and an isopentylidene group. Among these, an isopropylidene group may be used from the viewpoints of high-frequency characteristics (low dielectric constant, low dielectric loss tangent), adhesion with conductors, heat resistance, glass transition temperature, coefficient of thermal expansion, and flame retardancy.
Among the above options, W 2 may be an alkylene group having 1 to 5 carbon atoms or an alkylidene group having 2 to 5 carbon atoms.
q and r are each independently an integer of 0 to 4, and from the viewpoint of easy availability, each may be an integer of 0 to 2 or 0 or 2. When q or r is an integer of 2 or more, a plurality of R b2 s or a plurality of R b3 s may be the same or different.
The groups represented by general formula (III-1) represented by W 2 are as follows.
Figure JPOXMLDOC01-appb-C000024
（式中、Ｒｂ４及びＲｂ５は各々独立に、炭素数１～５の脂肪族炭化水素基又はハロゲン原子である。Ｗ３は炭素数１～５のアルキレン基、イソプロピリデン基、エーテル基、スルフィド基、スルホニル基、カルボニルオキシ基、ケト基又は単結合である。ｓ及びｔは各々独立に０～４の整数である。）
　Ｒｂ４及びＲｂ５が表す炭素数１～５の脂肪族炭化水素基、ハロゲン原子としては、Ｒｂ１の場合と同様に説明される。
　Ｗ３が表す炭素数１～５のアルキレン基、炭素数２～５のアルキリデン基としては、Ｗ２が表す炭素数１～５のアルキレン基、炭素数２～５のアルキリデン基と同じものが挙げられる。
　Ｗ３としては、上記選択肢の中から、炭素数２～５のアルキリデン基を選択してもよい。
　ｓ及びｔは０～４の整数であり、入手容易性の観点から、いずれも、０～２の整数であってもよく、０又は１であってもよく、０であってもよい。ｓ又はｔが２以上の整数である場合、複数のＲｂ４同士又はＲｂ５同士は、それぞれ同一であっても異なっていてもよい。
Figure JPOXMLDOC01-appb-C000024
(In the formula, R b4 and R b5 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. W 3 is an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, an ether group, It is a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group or a single bond. S and t are each independently an integer of 0 to 4.)
The aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R b4 and R b5 are the same as those described for R b1 .
Examples of the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by W 3 include the same ones as the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by W 2. Be done.
As W 3 , an alkylidene group having 2 to 5 carbon atoms may be selected from the above options.
s and t are integers of 0 to 4, and from the viewpoint of easy availability, each may be an integer of 0 to 2, 0 or 1, or 0. When s or t is an integer of 2 or more, the plurality of R b4 s or the plurality of R b5 s may be the same or different.
Figure JPOXMLDOC01-appb-C000025
（式中、ｎは０～１０の整数である。）
　ｎは、入手容易性の観点から、０～５の整数であってもよく、０～３の整数であってもよい。
Figure JPOXMLDOC01-appb-C000025
(In the formula, n is an integer of 0 to 10.)
From the viewpoint of easy availability, n may be an integer of 0 to 5 or an integer of 0 to 3.
Figure JPOXMLDOC01-appb-C000026
（式中、Ｒｂ６及びＲｂ７は各々独立に、水素原子又は炭素数１～５の脂肪族炭化水素基である。ｕは１～８の整数である。）
　Ｒｂ６及びＲｂ７が表す炭素数１～５の脂肪族炭化水素基としては、Ｒｂ１の場合と同様に説明される。
　ｕは１～８の整数であり、１～３の整数であってもよく、１であってもよい。
Figure JPOXMLDOC01-appb-C000026
(In the formula, R b6 and R b7 are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. U is an integer of 1 to 8.)
The aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R b6 and R b7 is explained in the same manner as in the case of R b1 .
u is an integer of 1 to 8, may be an integer of 1 to 3, and may be 1.
　前記一般式（Ｂ－１）及び（Ｂ－２）中のＸＢ１としては、導体との接着性、耐熱性、ガラス転移温度、熱膨張係数、難燃性、及び１０ＧＨｚ帯以上の高周波数帯における誘電特性の観点から、下記式（ＸＢ１－１）～（ＸＢ１－３）のいずれかで表される基であることが好ましく、下記式（ＸＢ１－３）で表される基であることがより好ましい。また、１０ＧＨｚ帯以上の高周波数帯における誘電特性の観点から、ＸＢ１として、下記式（ＸＢ１－１）で表される基と下記式（ＸＢ１－３）で表される基との両方を有していてもよいし、ＸＢ１として、下記式（ＸＢ１－２）で表される基と下記式（ＸＢ１－３）で表される基との両方を有していてもよい。
Figure JPOXMLDOC01-appb-C000027
（波線は、マレイミド基中の窒素原子との結合位置を示す。） X B1 in the general formulas (B-1) and (B-2) is, for example, adhesion to a conductor, heat resistance, glass transition temperature, coefficient of thermal expansion, flame retardancy, and high frequency band of 10 GHz or higher. From the viewpoint of the dielectric property in, a group represented by any of the following formulas (X B1 -1) to (X B1 -3) is preferable, and a group represented by the following formula (X B1 -3) More preferably. From the viewpoint of dielectric characteristics in a high frequency band of 10 GHz band or higher, both X B1 is a group represented by the following formula (X B1 -1) and a group represented by the following formula (X B1 -3). it may have a, as X B1, may have both a group represented by the group and the following formula represented by the following formula (X B1 -2) (X B1 -3) ..
Figure JPOXMLDOC01-appb-C000027
(The wavy line indicates the bonding position with the nitrogen atom in the maleimide group.)
　マレイミド化合物（Ｂ）中における（ｂ１）成分由来の構造単位の合計含有量は、５～９５質量％が好ましく、３０～９３質量％がより好ましく、６０～９０質量％がさらに好ましく、７５～９０質量％が特に好ましい。（ｂ１）成分由来の構造単位の含有量が上記範囲内であると、１０ＧＨｚ帯以上の高周波数帯における誘電特性がより良好となり、且つ、良好なフィルムハンドリング性が得られる傾向にある。 The total content of the structural units derived from the component (b1) in the maleimide compound (B) is preferably 5 to 95% by mass, more preferably 30 to 93% by mass, further preferably 60 to 90% by mass, and 75 to 90% by mass. Mass% is particularly preferred. When the content of the structural unit derived from the component (b1) is within the above range, the dielectric property in the high frequency band of 10 GHz band or higher tends to be better, and the good film handling property tends to be obtained.
　前記（ｂ２）成分は、アミノ基を２個有する化合物であれば、特に制限はない。
　（ｂ２）成分としては、例えば、４，４’－ジアミノジフェニルメタン、４，４’－ジアミノ－３，３’－ジメチルジフェニルメタン、４，４’－ジアミノ－３，３’－ジエチルジフェニルメタン、４，４’－ジアミノジフェニルエーテル、４，４’－ジアミノジフェニルスルホン、３，３’－ジアミノジフェニルスルホン、４，４’－ジアミノジフェニルケトン、４，４’－ジアミノビフェニル、３，３’－ジメチル－４，４’－ジアミノビフェニル、２，２’－ジメチル－４，４’－ジアミノビフェニル、３，３’－ジヒドロキシベンジジン、２，２－ビス（３－アミノ－４－ヒドロキシフェニル）プロパン、３，３’－ジメチル－５，５’－ジエチル－４，４’－ジアミノジフェニルメタン、２，２－ビス（４－アミノフェニル）プロパン、２，２－ビス［４－（４－アミノフェノキシ）フェニル］プロパン、１，３－ビス（３－アミノフェノキシ）ベンゼン、１，３－ビス（４－アミノフェノキシ）ベンゼン、１，４－ビス（４－アミノフェノキシ）ベンゼン、４，４’－ビス（４－アミノフェノキシ）ビフェニル、１，３－ビス〔１－［４－（４－アミノフェノキシ）フェニル］－１－メチルエチル〕ベンゼン、１，４－ビス〔１－［４－（４－アミノフェノキシ）フェニル］－１－メチルエチル〕ベンゼン、４，４’－［１，３－フェニレンビス（１－メチルエチリデン）］ビスアニリン、４，４’－［１，４－フェニレンビス（１－メチルエチリデン）］ビスアニリン、３，３’－［１，３－フェニレンビス（１－メチルエチリデン）］ビスアニリン、ビス［４－（４－アミノフェノキシ）フェニル］スルホン、ビス［４－（３－アミノフェノキシ）フェニル］スルホン、９，９－ビス（４－アミノフェニル）フルオレン等が挙げられる。 The component (b2) is not particularly limited as long as it is a compound having two amino groups.
Examples of the component (b2) 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 (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4, 4'-bis (4-aminophenoxy) biphenyl, 1,3-bis [1- [4- (4-aminophenoxy) phenyl] -1-methylethyl] benzene, 1,4-bis [1- [4- (4-Aminophenoxy) phenyl] -1-methylethyl] benzene, 4,4 ′-[1,3-phenylenebis (1-methylethylidene)] bisaniline, 4,4 ′-[1,4-phenylenebis ( 1-methylethylidene)] bisaniline, 3,3 ′-[1,3-phenylenebis (1-methylethylidene)] bisaniline, bis [4- (4-aminophenoxy) phenyl Sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 9,9-bis (4-aminophenyl) fluorene, and the like.
　これらの中でも、（ｂ２）成分としては、有機溶媒への溶解性、（ｂ１）成分との反応性、及び耐熱性に優れるという観点から、４，４’－ジアミノジフェニルメタン、４，４’－ジアミノ－３，３’－ジメチルジフェニルメタン、４，４’－ジアミノ－３，３’－ジエチルジフェニルメタン、２，２－ビス［４－（４－アミノフェノキシ）フェニル］プロパン、４，４’－［１，３－フェニレンビス（１－メチルエチリデン）］ビスアニリン、及び４，４’－［１，４－フェニレンビス（１－メチルエチリデン）］ビスアニリンが好ましい。また、（ｂ２）成分は、１０ＧＨｚ帯以上の高周波数帯における誘電特性及び低吸水性に優れるという観点から、３，３’－ジメチル－５，５’－ジエチル－４，４’－ジアミノジフェニルメタンが好ましい。また、（ｂ２）成分は、導体との高接着性、伸び、破断強度等の機械特性に優れる観点から、２，２－ビス［４－（４－アミノフェノキシ）フェニル］プロパンが好ましい。さらに、上記の有機溶媒への溶解性、合成時の反応性、耐熱性、導体との高接着性に優れることに加えて、１０ＧＨｚ帯以上の高周波数帯における誘電特性及び低吸湿性に優れるという観点から、（ｂ２）成分は、４，４’－［１，３－フェニレンビス（１－メチルエチリデン）］ビスアニリン、４，４’－［１，４－フェニレンビス（１－メチルエチリデン）］ビスアニリンが好ましい。 Among these, as the component (b2), 4,4′-diaminodiphenylmethane and 4,4′-diamino are preferable as they are excellent in solubility in an organic solvent, reactivity with the component (b1), and heat resistance. -3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 4,4 '-[1, 3-Phenylenebis (1-methylethylidene)] bisaniline and 4,4 ′-[1,4-phenylenebis (1-methylethylidene)] bisaniline are preferred. Further, the component (b2) is 3,3′-dimethyl-5,5′-diethyl-4,4′-diaminodiphenylmethane from the viewpoint of excellent dielectric properties and low water absorption in the high frequency band of 10 GHz or higher. preferable. Further, the component (b2) is preferably 2,2-bis [4- (4-aminophenoxy) phenyl] propane, from the viewpoint of excellent adhesiveness with a conductor, mechanical properties such as elongation and breaking strength. Further, in addition to being excellent in solubility in the above organic solvent, reactivity during synthesis, heat resistance, and high adhesiveness with a conductor, it is also excellent in dielectric properties and low hygroscopicity in a high frequency band of 10 GHz band or more. From the viewpoint, the component (b2) is 4,4 ′-[1,3-phenylenebis (1-methylethylidene)] bisaniline, 4,4 ′-[1,4-phenylenebis (1-methylethylidene)] bisaniline. Is preferred.
　（ｂ２）成分由来の構造単位としては、例えば、下記一般式（Ｂ－３）で表される基及び下記一般式（Ｂ－４）で表される基からなる群から選択される少なくとも１種類が挙げられる。 The structural unit derived from the component (b2) is, for example, at least one selected from the group consisting of a group represented by the following general formula (B-3) and a group represented by the following general formula (B-4). Is mentioned.
Figure JPOXMLDOC01-appb-C000028
（式中、ＸＢ２は有機基を示し、＊は他の構造への結合位置を示す。）
Figure JPOXMLDOC01-appb-C000028
(In the formula, X B2 represents an organic group, and * represents a bonding position to another structure.)
　前記一般式（Ｂ－３）及び（Ｂ－４）中のＸＢ２は有機基であり、（ｂ２）成分の残基に相当する。なお、（ｂ２）成分の残基とは、（ｂ２）成分から結合に供された官能基、つまりアミノ基を除いた部分の構造をいう。 X B2 in the general formulas (B-3) and (B-4) is an organic group and corresponds to the residue of the component (b2). In addition, the residue of the component (b2) refers to the structure of the portion excluding the functional group provided for binding, that is, the amino group, from the component (b2).
　前記一般式（Ｂ－３）及び前記一般式（Ｂ－４）中のＸＢ２は、下記一般式（VI）で表される基であることが好ましい。
Figure JPOXMLDOC01-appb-C000029
（式中、Ｒｂ１１及びＲｂ１２は各々独立に、炭素数１～５の脂肪族炭化水素基、炭素数１～５のアルコキシ基、水酸基又はハロゲン原子である。Ｗ４は、炭素数１～５のアルキレン基、炭素数２～５のアルキリデン基、エーテル基、スルフィド基、スルホニル基、カルボニルオキシ基、ケト基、フルオレニレン基、単結合、又は下記一般式（VI-1）もしくは（VI-2）で表される基である。ｑ’及びｒ’は各々独立に０～４の整数である。） X B2 in the general formula (B-3) and the general formula (B-4) is preferably a group represented by the following general formula (VI).
Figure JPOXMLDOC01-appb-C000029
(In the formula, R b11 and R b12 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group or a halogen atom. W 4 is 1 to 5 carbon atoms. 5 alkylene group, C 2-5 alkylidene group, ether group, sulfide group, sulfonyl group, carbonyloxy group, keto group, fluorenylene group, single bond, or the following general formula (VI-1) or (VI-2 ), Q'and r'are each independently an integer of 0 to 4.)
Figure JPOXMLDOC01-appb-C000030
（式中、Ｒｂ１３及びＲｂ１４は各々独立に、炭素数１～５の脂肪族炭化水素基又はハロゲン原子である。Ｗ５は炭素数１～５のアルキレン基、イソプロピリデン基、ｍ－フェニレンジイソプロピリデン基、ｐ－フェニレンジイソプロピリデン基、エーテル基、スルフィド基、スルホニル基、カルボニルオキシ基、ケト基又は単結合である。ｓ’及びｔ’は各々独立に０～４の整数である。）
Figure JPOXMLDOC01-appb-C000030
(In the formula, R b13 and R b14 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. W 5 is an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, or m-phenylene. It is a diene isopropylidene group, a p-phenylene diisopropylidene group, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group or a single bond, and s'and t'are each independently an integer of 0 to 4. .)
Figure JPOXMLDOC01-appb-C000031
（式中、Ｒｂ１５は炭素数１～５の脂肪族炭化水素基又はハロゲン原子である。Ｗ６及びＷ７は各々独立に、炭素数１～５のアルキレン基、イソプロピリデン基、エーテル基、スルフィド基、スルホニル基、カルボニルオキシ基、ケト基又は単結合である。ｗは０～４の整数である。）
Figure JPOXMLDOC01-appb-C000031
(In the formula, R b15 is an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. W 6 and W 7 are each independently an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, an ether group, It is a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group or a single bond, and w is an integer of 0 to 4.)
　上記一般式（VI）、（VI-1）又は（VI-2）中のＲｂ１１、Ｒｂ１２、Ｒｂ１３、Ｒｂ１４及びＲｂ１５が表す炭素数１～５の脂肪族炭化水素基又はハロゲン原子としては、前記一般式（II）中のＲｂ１と同じものが挙げられる。該脂肪族炭化水素基としては、炭素数１～３の脂肪族炭化水素基であってもよく、メチル基、エチル基であってもよい。
　上記一般式（VII）、（VII-1）又は（VII-2）中のＷ４及びＷ５が表す炭素数１～５のアルキレン基、並びにＷ４が表す炭素数２～５のアルキリデン基としては、前記一般式（III）中のＷ２の場合と同様に説明される。また、上記一般式（VII-2）中のＷ６及びＷ７が表す炭素数１～５のアルキレン基は、前記一般式（III）中のＷ２の場合と同様に説明される。
　ｑ’及びｒ’は０～４の整数であり、入手容易性の観点から、いずれも、０～２の整数であってもよく、０又は２であってもよい。ｓ’及びｔ’は０～４の整数であり、入手容易性の観点から、いずれも、０～２の整数であってもよく、０又は１であってもよく、０であってもよい。ｗは０～４の整数であり、入手容易性の観点から、０～２の整数であってもよく、０であってもよい。 The general formula (VI), (VI-1 ) or (VI-2) R b11, R b12, R b13, R b14 and aliphatic hydrocarbon group, or a halogen atom having 1 to 5 carbon atoms represented by R b15 in Are the same as R b1 in the general formula (II). The aliphatic hydrocarbon group may be an aliphatic hydrocarbon group having 1 to 3 carbon atoms, or may be a methyl group or an ethyl group.
As the alkylene group having 1 to 5 carbon atoms represented by W 4 and W 5 in the general formula (VII), (VII-1) or (VII-2), and the alkylidene group having 2 to 5 carbon atoms represented by W 4. Is described in the same manner as in the case of W 2 in the general formula (III). The alkylene group having 1 to 5 carbon atoms represented by W 6 and W 7 in the general formula (VII-2) is explained in the same manner as in the case of W 2 in the general formula (III).
q ′ and r ′ are integers of 0 to 4, and from the viewpoint of easy availability, both may be integers of 0 to 2 or 0 or 2. s ′ and t ′ are integers of 0 to 4, and from the viewpoint of easy availability, each may be an integer of 0 to 2, 0 or 1, or 0. .. w is an integer of 0 to 4, and may be an integer of 0 to 2 or 0 from the viewpoint of easy availability.
　マレイミド化合物（Ｂ）中における（ｂ２）成分由来の構造単位の合計含有量は、５～９５質量％が好ましく、７～７０質量％がより好ましく、１０～４０質量％がさらに好ましく、１０～２５質量％が特に好ましい。成分（ｂ２）由来の構造単位の含有量が上記範囲内であると、１０ＧＨｚ帯以上の高周波数帯における誘電特性に優れ、且つより良好な耐熱性、難燃性及びガラス転移温度が得られる傾向にある。 The total content of the structural units derived from the component (b2) in the maleimide compound (B) is preferably 5 to 95% by mass, more preferably 7 to 70% by mass, further preferably 10 to 40% by mass. Mass% is particularly preferred. When the content of the structural unit derived from the component (b2) is within the above range, the dielectric properties in the high frequency band of 10 GHz or higher are excellent, and more favorable heat resistance, flame retardancy, and glass transition temperature tend to be obtained. It is in.
　マレイミド化合物（Ｂ）中における（ｂ１）成分由来の構造単位と、（ｂ２）成分由来の構造単位との含有比率は、マレイミド化合物（Ｂ）中における、（ｂ２）成分の－ＮＨ２基由来の基（－ＮＨ２も含む）の合計当量（Ｔａ２）と、（ｂ１）成分に由来するマレイミド基由来の基（マレイミド基も含む）の合計当量（Ｔａ１）との当量比（Ｔａ２／Ｔａ１）が、０．０５～１０であることが好ましく、１．０～５であることがより好ましい。当量比（Ｔａ２／Ｔａ１）が上記範囲内であると、１０ＧＨｚ帯以上の高周波数帯における誘電特性に優れ、且つより良好な耐熱性、難燃性及びガラス転移温度が得られる傾向にある。 The content ratio of the structural unit derived from the component (b1) and the structural unit derived from the component (b2) in the maleimide compound (B) is calculated from the —NH 2 group derived from the component (b2) in the maleimide compound (B). The equivalent ratio (Ta2 / Ta1) between the total equivalent (Ta2) of the group (including —NH 2 ) and the total equivalent (Ta1) of the group (including the maleimide group) derived from the maleimide group derived from the component (b1) is , 0.05 to 10 is preferable, and 1.0 to 5 is more preferable. When the equivalent ratio (Ta2 / Ta1) is in the above range, the dielectric properties in the high frequency band of 10 GHz or higher are excellent, and more favorable heat resistance, flame retardancy and glass transition temperature tend to be obtained.
　マレイミド化合物（Ｂ）は、１０ＧＨｚ帯以上の高周波数帯における誘電特性の観点、並びに有機溶媒への溶解性、導体との高接着性及びフィルムの成形性等の観点から、下記一般式（Ｂ－５）で表されるポリアミノビスマレイミド化合物を含むことが好ましい。 The maleimide compound (B) is represented by the following general formula (B-, from the viewpoint of dielectric properties in a high frequency band of 10 GHz or higher, the solubility in an organic solvent, the high adhesion with a conductor, the moldability of a film, etc. It is preferable to include a polyamino bismaleimide compound represented by 5).
Figure JPOXMLDOC01-appb-C000032
（式中、ＸＢ１及びＸＢ２は、上記で説明したとおりである。）
Figure JPOXMLDOC01-appb-C000032
(In the formula, X B1 and X B2 are as described above.)
（ポリアミノビスマレイミド化合物（Ｂ１）の製造方法）
　前記マレイミド化合物（ｂ１）由来の構造単位とジアミン化合物（ｂ２）由来の構造単位とを有する前記ポリアミノビスマレイミド化合物（Ｂ１）は、例えば、（ｂ１）成分と（ｂ２）成分とを有機溶媒中で反応させることで製造することができる。
　（ｂ１）成分と（ｂ２）成分とを反応させてポリアミノビスマレイミド化合物（Ｂ１）を製造する際には、必要に応じて反応触媒を使用することもできる。反応触媒としては、制限されるものではないが、例えば、ｐ－トルエンスルホン酸等の酸性触媒；トリエチルアミン、ピリジン、トリブチルアミン等のアミン類；メチルイミダゾール、フェニルイミダゾール等のイミダゾール類；トリフェニルホスフィン等のリン系触媒などが挙げられる。これらは１種類を単独で使用してもよいし、２種類以上を併用してもよい。また、反応触媒の配合量に特に制限はないが、例えば、（ｂ１）成分及び（ｂ２）成分の合計量１００質量部に対して、０．０１～５質量部使用すればよい。 (Method for producing polyaminobismaleimide compound (B1))
The polyamino bismaleimide compound (B1) having the structural unit derived from the maleimide compound (b1) and the structural unit derived from the diamine compound (b2) is, for example, a component (b1) and a component (b2) in an organic solvent. It can be produced by reacting.
When the component (b1) and the component (b2) are reacted with each other to produce the polyamino bismaleimide compound (B1), a reaction catalyst may be used, if necessary. Examples of the reaction catalyst include, but are not limited to, acidic catalysts such as p-toluenesulfonic acid; amines such as triethylamine, pyridine and tributylamine; imidazoles such as methylimidazole and phenylimidazole; triphenylphosphine and the like. Examples of the phosphorus-based catalysts include These may be used alone or in combination of two or more. The amount of the reaction catalyst blended is not particularly limited, but may be, for example, 0.01 to 5 parts by mass based on 100 parts by mass of the total amount of the components (b1) and (b2).
　（ｂ１）成分、（ｂ２）成分、必要によりその他の成分を合成釜に所定量仕込み、（ｂ１）成分と（ｂ２）成分とをマイケル付加反応させることにより、前記ポリアミノビスマレイミド化合物が得られる。この工程での反応条件としては、特に限定されないが、例えば、反応速度等の作業性、ゲル化抑制などの観点から、反応温度は５０～１６０℃が好ましく、反応時間は１～１０時間が好ましい。
　また、この工程では有機溶媒を追加又は濃縮して反応原料の固形分濃度及び溶液粘度を調整することができる。反応原料の固形分濃度は、特に限定されないが、例えば、１０～９０質量％が好ましく、２０～８０質量％がより好ましい。反応原料の固形分濃度が１０質量％以上の場合、反応速度が遅くなりすぎず、製造コストの面で有利となる傾向にある。また、反応原料の固形分濃度が９０質量％以下の場合、より良好な溶解性が得られ、撹拌効率が良くなり、ゲル化し難い傾向にある。 The polyamino bismaleimide compound is obtained by charging a predetermined amount of the component (b1), the component (b2) and, if necessary, other components into a synthesis kettle and subjecting the component (b1) and the component (b2) to a Michael addition reaction. The reaction conditions in this step are not particularly limited, but the reaction temperature is preferably 50 to 160 ° C., and the reaction time is preferably 1 to 10 hours from the viewpoints of workability such as reaction rate and suppression of gelation. ..
Further, in this step, the solid content concentration and solution viscosity of the reaction raw material can be adjusted by adding or concentrating the organic solvent. The solid content concentration of the reaction raw material is not particularly limited, but for example, preferably 10 to 90% by mass, more preferably 20 to 80% by mass. When the solid content concentration of the reaction raw material is 10% by mass or more, the reaction rate does not become too slow, and the production cost tends to be advantageous. Further, when the solid content concentration of the reaction raw material is 90% by mass or less, better solubility is obtained, stirring efficiency is improved, and gelation tends to be difficult.
　こうして得られるポリアミノビスマレイミド化合物（Ｂ１）の数平均分子量は、特に限定されないが、４００～１０，０００が好ましく、５００～５，０００がより好ましく、５００～２，０００がさらに好ましく、５００～１，３００が特に好ましい。ポリアミノビスマレイミド化合物（Ｂ１）の数平均分子量は、実施例に記載の方法により求めることができる。 The number average molecular weight of the polyamino bismaleimide compound (B1) thus obtained is not particularly limited, but is preferably 400 to 10,000, more preferably 500 to 5,000, further preferably 500 to 2,000, and 500 to 1 , 300 is particularly preferred. The number average molecular weight of the polyamino bismaleimide compound (B1) can be determined by the method described in Examples.
（（Ａ）成分及び（Ｂ）成分の含有量、並びにそれらの含有割合）
　本発明の樹脂組成物において、前記（Ａ）成分の含有量に特に制限はないが、１０ＧＨｚ帯以上の高周波数帯における誘電特性の観点から、樹脂組成物中の樹脂成分の総和１００質量部に対して１質量部以上であることが好ましく、１～２０質量部であることがより好ましく、３～１０質量部であることがさらに好ましく、３～７質量部であることが特に好ましい。ここで、本明細書において、「樹脂成分」とは、前記（Ａ）成分及び（Ｂ）成分、さらに、任意に使用する（Ｃ）成分及び（Ｇ）成分のことを指す。つまり、樹脂組成物が（Ｃ）成分及び（Ｇ）成分を含有しない場合には、「樹脂成分」は（Ａ）成分及び（Ｂ）成分を指し、樹脂組成物が（Ｃ）成分及び（Ｇ）成分からなる群から選択される少なくとも１種類を含有する場合には、「樹脂成分」には、（Ａ）成分及び（Ｂ）成分と共に、さらに含有するそれらの成分が含まれる。
　前記（Ｂ）成分の含有量は特に制限はないが、１０ＧＨｚ帯以上の高周波数帯における誘電特性及び成形性の観点から、樹脂組成物中の樹脂成分の総和１００質量部に対して、１０～９０質量部であることが好ましく、２０～８０質量部であることがより好ましく、３０～７０質量部であることがさらに好ましく、３５～６０質量部であることが特に好ましい。
　前記（Ａ）成分と前記（Ｂ）成分の含有割合［（Ａ）／（Ｂ）］は特に制限はないが、質量比で、１／９９～８０／２０であってもよく、３／９７～７５／２５であってもよく、５／９５～７０／３０であってもよく、５／９５～５０／５０であってもよく、５／９５～２０／８０であってもよく、５／９５～１５／８５であってもよい。（Ａ）成分と（Ｂ）成分の合計量に対する（Ａ）成分の含有割合が１質量％以上であれば、１０ＧＨｚ帯以上の高周波数帯において優れた誘電特性が得られる傾向にある。また、８０質量％以下であれば、耐熱性、成形性及び加工性が優れる傾向にある。 (Contents of (A) component and (B) component, and their content ratio)
In the resin composition of the present invention, the content of the component (A) is not particularly limited, but from the viewpoint of dielectric properties in a high frequency band of 10 GHz or higher, the total amount of the resin components in the resin composition is 100 parts by mass. On the other hand, it is preferably 1 part by mass or more, more preferably 1 to 20 parts by mass, further preferably 3 to 10 parts by mass, and particularly preferably 3 to 7 parts by mass. Here, in the present specification, the “resin component” refers to the above-mentioned components (A) and (B), and optionally the components (C) and (G). That is, when the resin composition does not contain the components (C) and (G), the “resin component” refers to the components (A) and (B), and the resin composition includes the components (C) and (G). When at least one kind selected from the group consisting of the components) is contained, the “resin component” includes the components (A) and (B) as well as those components further contained.
The content of the component (B) is not particularly limited, but from the viewpoint of dielectric properties and moldability in a high frequency band of 10 GHz or higher, it is 10 to 10 parts by mass based on 100 parts by mass of the resin components in the resin composition. The amount is preferably 90 parts by mass, more preferably 20 to 80 parts by mass, further preferably 30 to 70 parts by mass, and particularly preferably 35 to 60 parts by mass.
The content ratio [(A) / (B)] of the component (A) and the component (B) is not particularly limited, but may be 1/99 to 80/20 in mass ratio, and may be 3/97. To 75/25, 5/95 to 70/30, 5/95 to 50/50, 5/95 to 20/80, 5 It may be / 95 to 15/85. When the content ratio of the component (A) to the total amount of the component (A) and the component (B) is 1% by mass or more, excellent dielectric properties tend to be obtained in a high frequency band of 10 GHz band or higher. Further, if it is 80% by mass or less, heat resistance, moldability and workability tend to be excellent.
＜その他の成分＞
　本発明の一態様の樹脂組成物は、さらにその他の成分を含有してなるものであってもよい。その他の成分としては、例えば、スチレン系熱可塑性エラストマー（Ｃ）［以下、（Ｃ）成分と称することがある。］、無機充填材（Ｄ）［以下、（Ｄ）成分と称することがある。］、硬化促進剤（Ｅ）［以下、（Ｅ）成分と称することがある。］、難燃剤（Ｆ）［以下、（Ｆ）成分と称することがある。］及び架橋剤（Ｇ）から選択される少なくとも１種類が挙げられる。これらを含有させることにより、積層板とした際の諸特性をさらに向上させることができる。
　以下、これらの成分について詳述する。 <Other ingredients>
The resin composition of one aspect of the present invention may further contain other components. As the other component, for example, a styrene-based thermoplastic elastomer (C) [hereinafter, may be referred to as a component (C). ], Inorganic filler (D) [Hereinafter, it may be called a (D) component. ], A hardening accelerator (E) [Hereinafter, it may be called a (E) component. ], A flame retardant (F) [Hereinafter, it may be called a (F) component. ] And at least one type selected from a crosslinking agent (G). By including these, it is possible to further improve various properties of the laminated plate.
Hereinafter, these components will be described in detail.
（スチレン系熱可塑性エラストマー（Ｃ））
　本発明の樹脂組成物にスチレン系熱可塑性エラストマ（Ｃ）を含有させることにより、１０ＧＨｚ帯以上の高周波数帯における誘電特性、成形性、導体との接着性、はんだ耐熱性、ガラス転移温度、熱膨張係数及び難燃性において良好となり、これらのバランスが良くなる傾向にある。
　スチレン系熱可塑性エラストマー（Ｃ）としては、下記一般式で表されるスチレン系化合物由来の構造単位（下記参照）を有する熱可塑性エラストマーであれば特に制限はなく、スチレン由来の構造単位（Ｒｃ１＝水素原子、ｋ＝０）を有する熱可塑性エラストマーであってもよい。
Figure JPOXMLDOC01-appb-C000033
（上記式中、Ｒｃ１は水素原子又は炭素数１～５のアルキル基であり、Ｒｃ２は、炭素数１～５のアルキル基である。ｋは、０～５の整数である。）
　Ｒｃ１及びＲｃ２が表す炭素数１～５のアルキル基としては、例えば、メチル基、エチル基、ｎ－プロピル基等が挙げられ、炭素数１～３のアルキル基であってもよく、メチル基であってもよい。
　Ｒｃ１は、水素原子であってもよい。
　ｋは、０～２の整数であってもよく、０又は１であってもよく、０であってもよい。 (Styrene-based thermoplastic elastomer (C))
By incorporating the styrene-based thermoplastic elastomer (C) in the resin composition of the present invention, dielectric properties in a high frequency band of 10 GHz or higher, moldability, adhesiveness with a conductor, solder heat resistance, glass transition temperature, heat The expansion coefficient and flame retardancy are good, and the balance between them tends to be good.
The styrene-based thermoplastic elastomer (C) is not particularly limited as long as it is a thermoplastic elastomer having a structural unit derived from a styrene compound represented by the following general formula (see below), and a structural unit derived from styrene (R c1 = Hydrogen atom, k = 0).
Figure JPOXMLDOC01-appb-C000033
(In the above formula, R c1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R c2 is an alkyl group having 1 to 5 carbon atoms, and k is an integer of 0 to 5.)
Examples of the alkyl group having 1 to 5 carbon atoms represented by R c1 and R c2 include a methyl group, an ethyl group, an n-propyl group, and the like, which may be an alkyl group having 1 to 3 carbon atoms. It may be a group.
R c1 may be a hydrogen atom.
k may be an integer of 0 to 2, may be 0 or 1, and may be 0.
　スチレン系熱可塑性エラストマー（Ｃ）が有するスチレン系化合物由来の構造単位以外の構造単位としては、ブタジエン由来の構造単位、イソプレン由来の構造単位、マレイン酸由来の構造単位、無水マレイン酸由来の構造単位等が挙げられる。スチレン系熱可塑性エラストマー（Ｃ）は、１種類を単独で用いてもよいし、２種類以上を併用してもよい。
　前記ブタジエン由来の構造単位及び前記イソプレン由来の構造単位は、水素添加されていてもよい。水素添加されている場合、ブタジエン由来の構造単位はエチレン単位とブチレン単位とが混合した構造単位となり、イソプレン由来の構造単位はエチレン単位とプロピレン単位とが混合した構造単位となる。 As the structural unit other than the structural unit derived from the styrene compound included in the styrene-based thermoplastic elastomer (C), a structural unit derived from butadiene, a structural unit derived from isoprene, a structural unit derived from maleic acid, a structural unit derived from maleic anhydride Etc. As the styrene-based thermoplastic elastomer (C), one type may be used alone, or two or more types may be used in combination.
The butadiene-derived structural unit and the isoprene-derived structural unit may be hydrogenated. When hydrogenated, the structural unit derived from butadiene is a structural unit in which ethylene units and butylene units are mixed, and the structural unit derived from isoprene is a structural unit in which ethylene units and propylene units are mixed.
　スチレン系熱可塑性エラストマー（Ｃ）としては、１０ＧＨｚ帯以上の高周波数帯における誘電特性、導体との接着性、耐熱性、ガラス転移温度及び熱膨張係数の観点から、スチレン－ブタジエン－スチレンブロック共重合体の水素添加物（ＳＥＢＳ、ＳＢＢＳ）、スチレン－イソプレン－スチレンブロック共重合体の水素添加物（ＳＥＰＳ）及びスチレン－無水マレイン酸共重合体（ＳＭＡ）からなる群から選択される少なくとも１種類であることが好ましく、スチレン－ブタジエン－スチレンブロック共重合体の水素添加物（ＳＥＢＳ）及びスチレン－イソプレン－スチレンブロック共重合体の水素添加物（ＳＥＰＳ）からなる群から選択される少なくとも１種類であることががより好ましい。 As the styrene-based thermoplastic elastomer (C), a styrene-butadiene-styrene block copolymer is used in view of dielectric properties in a high frequency band of 10 GHz band or higher, adhesiveness with a conductor, heat resistance, glass transition temperature and coefficient of thermal expansion. At least one selected from the group consisting of a combined hydrogenated product (SEBS, SBBS), a styrene-isoprene-styrene block copolymer hydrogenated product (SEPS), and a styrene-maleic anhydride copolymer (SMA). Preferably, it is at least one selected from the group consisting of hydrogenated products of styrene-butadiene-styrene block copolymer (SEBS) and hydrogenated products of styrene-isoprene-styrene block copolymer (SEPS). Is more preferable.
　なお、前記スチレン－ブタジエン－スチレンブロック共重合体の水素添加物としては、炭素－炭素二重結合の水素添加率が通常９０％以上（９５％以上であってもよい。）であるＳＥＢＳと、ブタジエンブロック中の１，２－結合部位の炭素－炭素二重結合（下記左参照）が部分的に水素添加されたＳＢＢＳ（全体の炭素－炭素二重結合に対する水素添加率はおよそ６０～８５％）とがある。つまり、ＳＢＢＳについては架橋性能を有する可能性があり、その場合、後述する架橋剤（Ｇ）に含まれ得るが、本発明においてはたとえ架橋性能を有していても、スチレン系熱可塑性エラストマーについては（Ｃ）成分に分類する。該（Ｃ）成分としては、架橋性能を有さないものであってもよく、つまり、水添スチレン系熱可塑性エラストマーであってもよく、その水素転化率は、好ましくは７０％以上、より好ましくは８０％以上、さらに好ましくは９０％以上、特に好ましくは９５％以上、最も好ましくは９９％以上である。
Figure JPOXMLDOC01-appb-C000034
 As the hydrogenated product of the styrene-butadiene-styrene block copolymer, SEBS having a carbon-carbon double bond hydrogenation rate of usually 90% or more (or 95% or more) may be used, SBBS with partially hydrogenated carbon-carbon double bonds at the 1,2-bonding sites in the butadiene block (see left below) (hydrogenation ratio of the total carbon-carbon double bonds is about 60-85%) ) There is. That is, SBBS may have cross-linking performance, and in that case, it may be contained in the cross-linking agent (G) described below, but in the present invention, even if it has cross-linking performance, the styrene-based thermoplastic elastomer is Is classified as a component (C). The component (C) may be one that does not have cross-linking performance, that is, may be a hydrogenated styrene thermoplastic elastomer, and its hydrogen conversion rate is preferably 70% or more, more preferably Is 80% or more, more preferably 90% or more, particularly preferably 95% or more, and most preferably 99% or more.
Figure JPOXMLDOC01-appb-C000034
　前記ＳＥＢＳにおいて、スチレン由来の構造単位の含有率（以下、スチレン含有率と略称することがある。）は、１０ＧＨｚ帯以上の高周波数帯における誘電特性、導体との接着性、耐熱性、ガラス転移温度及び熱膨張係数の観点から、５～８０質量％であってもよく、５～７０質量％であってもよく、１０～７０質量％であってもよく、１０～５０質量％であってもよい。ＳＥＢＳのメルトフローレート（ＭＦＲ）は、特に制限はないが、２３０℃、荷重２．１６ｋｇｆ（２１．２Ｎ）の測定条件では、０．１～２０ｇ／１０ｍｉｎであってもよく、０．５～１５ｇ／１０ｍｉｎであってもよい。
　ＳＥＢＳの市販品としては、例えば、旭化成ケミカルズ株式会社製のタフテック（登録商標）Ｈシリーズ、Ｍシリーズ、株式会社クラレ製のセプトン（登録商標）シリーズ、クレイトンポリマージャパン株式会社製のクレイトン（登録商標）Ｇポリマーシリーズ等が挙げられる。 In the SEBS, the content of the structural unit derived from styrene (hereinafter, may be abbreviated as styrene content) is dielectric properties in a high frequency band of 10 GHz band or higher, adhesiveness with a conductor, heat resistance, glass transition. From the viewpoint of temperature and coefficient of thermal expansion, it may be 5 to 80% by mass, 5 to 70% by mass, 10 to 70% by mass, or 10 to 50% by mass. Good. The melt flow rate (MFR) of SEBS is not particularly limited, but may be 0.1 to 20 g / 10 min under the measurement conditions of 230 ° C. and a load of 2.16 kgf (21.2 N), and 0.5 to It may be 15 g / 10 min.
Examples of commercially available products of SEBS include Tuftec (registered trademark) H series and M series manufactured by Asahi Kasei Chemicals Corporation, Septon (registered trademark) series manufactured by Kuraray Co., Ltd., and Kraton (registered trademark) manufactured by Kraton Polymer Japan Co., Ltd. G polymer series etc. are mentioned.
　前記ＳＢＢＳにおいて、スチレン含有率は、１０ＧＨｚ帯以上の高周波数帯における誘電特性、導体との接着性、耐熱性、ガラス転移温度及び熱膨張係数の観点から、４０～８０質量％であってもよく、５０～７５質量％であってもよく、５５～７５質量％であってもよい。ＳＢＢＳのメルトフローレート（ＭＦＲ）は、特に制限はないが、１９０℃、荷重２．１６ｋｇｆ（２１．２Ｎ）の測定条件では、０．１～１０ｇ／１０ｍｉｎであってもよく、０．５～１０ｇ／１０ｍｉｎであってもよく、１～６ｇ／１０ｍｉｎであってもよい。
　ＳＢＢＳの市販品としては、例えば、旭化成ケミカルズ株式会社製のタフテック（登録商標）Ｐシリーズ等が挙げられる。 In the SBBS, the styrene content may be 40 to 80 mass% from the viewpoint of dielectric properties in a high frequency band of 10 GHz band or higher, adhesiveness with a conductor, heat resistance, glass transition temperature and coefficient of thermal expansion. , 50 to 75% by mass, or 55 to 75% by mass. The melt flow rate (MFR) of SBBS is not particularly limited, but may be 0.1 to 10 g / 10 min under the measurement conditions of 190 ° C. and a load of 2.16 kgf (21.2 N), and 0.5 to It may be 10 g / 10 min or 1 to 6 g / 10 min.
Examples of commercial products of SBBS include Tuftec (registered trademark) P series manufactured by Asahi Kasei Chemicals Corporation.
　スチレン－イソプレン－スチレンブロック共重合体の水素添加物（ＳＥＰＳ）の水素添加率は、９０％以上であってもよく、９５％以上であってもよい。ＳＥＰＳにおいて、スチレン含有率は、１０ＧＨｚ帯以上の高周波数帯における誘電特性、導体との接着性、耐熱性、ガラス転移温度及び熱膨張係数の観点から、５～６０質量％であってもよく、５～５０質量％であってもよく、１０～４０質量％であってもよい。ＳＥＰＳのメルトフローレート（ＭＦＲ）は、特に制限はないが、２３０℃、荷重２．１６ｋｇｆ（２１．２Ｎ）の測定条件では、０．１～１３０ｇ／１０ｍｉｎであってもよく、１０～１００ｇ／１０ｍｉｎであってもよく、５０～９０ｇ／１０ｍｉｎであってもよい。
　ＳＥＰＳの市販品としては、例えば、株式会社クラレ製のセプトン（登録商標）シリーズ、クレイトンポリマージャパン株式会社製のクレイトンＧポリマーシリーズ等が挙げられる。 The hydrogenation rate of the hydrogenated product (SEPS) of the styrene-isoprene-styrene block copolymer may be 90% or more, or 95% or more. In SEPS, the styrene content may be 5 to 60 mass% from the viewpoint of dielectric properties in a high frequency band of 10 GHz band or higher, adhesiveness with a conductor, heat resistance, glass transition temperature and thermal expansion coefficient, It may be 5 to 50% by mass, or 10 to 40% by mass. The melt flow rate (MFR) of SEPS is not particularly limited, but may be 0.1 to 130 g / 10 min under the measurement conditions of 230 ° C. and a load of 2.16 kgf (21.2 N), and 10 to 100 g / It may be 10 min, or 50 to 90 g / 10 min.
Examples of commercially available SEPS include Septon (registered trademark) series manufactured by Kuraray Co., Ltd., Kraton G polymer series manufactured by Kraton Polymer Japan Co., Ltd., and the like.
　スチレン－無水マレイン酸共重合体（ＳＭＡ）において、スチレン含有率は、１０ＧＨｚ帯以上の高周波数帯における誘電特性、導体との接着性、耐熱性、ガラス転移温度及び熱膨張係数の観点から、２０～９０質量％であってもよく、４０～９０質量％であってもよく、５０～９０質量％であってもよく、５５～８５質量％であってもよい。
　スチレン－無水マレイン酸共重合体（ＳＭＡ）は、無水マレイン酸由来の構造単位がエステル化されていてもよい。
　ＳＭＡの市販品としては、クレイバレーテクノロジーＵＳＡ社製のＳＭＡ（登録商標）レジン等が挙げられる。
　なお、上記のスチレン系熱可塑性エラストマー（Ｃ）はいずれも市販品を用いればよい。上記スチレン含有率及びメルトフローレート（ＭＦＲ）は、製造会社のカタログ又はホームページに記載の値である。 In the styrene-maleic anhydride copolymer (SMA), the styrene content is 20 from the viewpoint of dielectric properties in a high frequency band of 10 GHz band or higher, adhesiveness with a conductor, heat resistance, glass transition temperature and thermal expansion coefficient. The amount may be up to 90% by mass, 40 to 90% by mass, 50 to 90% by mass, or 55 to 85% by mass.
The structural unit derived from maleic anhydride may be esterified in the styrene-maleic anhydride copolymer (SMA).
Examples of commercially available SMA products include SMA (registered trademark) resin manufactured by Clay Valley Technology USA.
A commercially available product may be used for each of the styrene-based thermoplastic elastomers (C). The styrene content and the melt flow rate (MFR) are values described in the manufacturer's catalog or website.
　本発明の樹脂組成物が（Ｃ）成分を含有する場合、（Ｃ）成分の含有量は、１０ＧＨｚ帯以上の高周波数帯における誘電特性、導体との接着性、耐熱性、ガラス転移温度及び熱膨張係数の観点から、（Ａ）～（Ｃ）成分の総和１００質量部に対して、５～６０質量部であることが好ましく、１０～６０質量部であることがより好ましく、１５～６０質量部であることがさらに好ましく、１５～５０質量部であることが特に好ましく、１５～４０質量部であることが最も好ましい。（Ｃ）成分の含有量が（Ａ）～（Ｃ）成分の総和１００質量部に対して５質部以上であれば、１０ＧＨｚ帯以上の高周波数帯における誘電特性及び耐吸湿性がより良好となる傾向にあり、６０質量部以下であれば、耐熱性、成形性、加工性及び難燃性がより良好となる傾向にある。 When the resin composition of the present invention contains the component (C), the content of the component (C) is such that dielectric properties in a high frequency band of 10 GHz band or higher, adhesiveness with a conductor, heat resistance, glass transition temperature and heat. From the viewpoint of the coefficient of expansion, it is preferably 5 to 60 parts by mass, more preferably 10 to 60 parts by mass, and 15 to 60 parts by mass with respect to 100 parts by mass as the total of the components (A) to (C). More preferably, it is 15 to 50 parts by mass, and most preferably 15 to 40 parts by mass. When the content of the component (C) is 5 parts by mass or more based on 100 parts by mass of the total amount of the components (A) to (C), the dielectric property and the moisture absorption resistance in the high frequency band of 10 GHz band or more are better. If it is 60 parts by mass or less, heat resistance, moldability, processability and flame retardancy tend to be better.
（無機充填材（Ｄ））
　本発明の樹脂組成物に無機充填材（Ｄ）を含有させることで、低熱膨張係数、高弾性率性、耐熱性及び難燃性を向上させることができる傾向にある。
　（Ｄ）成分としては、特に制限されるものではないが、例えば、シリカ、アルミナ、酸化チタン、マイカ、ベリリア、チタン酸バリウム、チタン酸カリウム、チタン酸ストロンチウム、チタン酸カルシウム、炭酸アルミニウム、水酸化マグネシウム、水酸化アルミニウム、ケイ酸アルミニウム、炭酸カルシウム、ケイ酸カルシウム、ケイ酸マグネシウム、窒化ケイ素、窒化ホウ素、クレー（焼成クレー等）、タルク、ホウ酸アルミニウム、炭化ケイ素等が挙げられる。これらは１種類を単独で用いてもよく、２種類以上を併用してもよい。これらの中でも、熱膨張係数、弾性率、耐熱性及び難燃性の観点から、シリカ、アルミナ、マイカ、タルクであってもよく、シリカ、アルミナであってもよく、シリカであってもよい。シリカとしては、例えば、湿式法で製造され含水率の高い沈降シリカと、乾式法で製造され結合水等をほとんど含まない乾式法シリカが挙げられ、乾式法シリカとしては、さらに、製造法の違いにより破砕シリカ、フュームドシリカ、溶融シリカ（溶融球状シリカ）が挙げられる。
　また、無機充填材（Ｄ）の形状及び粒径についても特に制限はない。例えば、粒径は０．０１～２０μｍであってもよく、０．１～１０μｍであってもよい。ここで、粒径とは、平均粒子径を指し、粒子の全体積を１００％として粒子径による累積度数分布曲線を求めた時、体積５０％に相当する点の粒子径のことである。レーザ回折散乱法を用いた粒度分布測定装置等で測定することができる。 (Inorganic filler (D))
By including the inorganic filler (D) in the resin composition of the present invention, the low thermal expansion coefficient, high elastic modulus, heat resistance and flame retardancy tend to be improved.
The component (D) is not particularly limited, but examples thereof include silica, alumina, titanium oxide, mica, beryllia, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, and hydroxide. Examples thereof include magnesium, aluminum hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay (calcined clay and the like), talc, aluminum borate, silicon carbide and the like. These may be used alone or in combination of two or more. Among these, silica, alumina, mica, talc, silica, alumina, or silica may be used from the viewpoint of thermal expansion coefficient, elastic modulus, heat resistance and flame retardancy. Examples of silica include precipitated silica having a high water content produced by a wet method, and dry method silica produced by a dry method and containing almost no bound water, and the like. Examples thereof include crushed silica, fumed silica, and fused silica (fused spherical silica).
The shape and particle size of the inorganic filler (D) are also not particularly limited. For example, the particle size may be 0.01 to 20 μm, or 0.1 to 10 μm. Here, the particle diameter refers to the average particle diameter, and is the particle diameter at a point corresponding to a volume of 50% when the cumulative frequency distribution curve based on the particle diameter is obtained with the total volume of the particles being 100%. It can be measured by a particle size distribution measuring device or the like using a laser diffraction scattering method.
　本発明の樹脂組成物が（Ｄ）成分を含有する場合、樹脂組成物中における（Ｄ）成分の含有量は特に制限されるものではないが、熱膨張係数、弾性率、耐熱性及び難燃性の観点から、樹脂成分の総和１００質量部に対して、好ましくは５～７０質量部、より好ましくは１５～７０質量部、さらに好ましくは２０～６０質量部、特に好ましくは３５～６０質量部、最も好ましくは４０～５５質量部である。 When the resin composition of the present invention contains the component (D), the content of the component (D) in the resin composition is not particularly limited, but the thermal expansion coefficient, the elastic modulus, the heat resistance and the flame retardancy. From the viewpoint of properties, preferably 5 to 70 parts by mass, more preferably 15 to 70 parts by mass, further preferably 20 to 60 parts by mass, particularly preferably 35 to 60 parts by mass, relative to 100 parts by mass of the total of the resin components. , And most preferably 40 to 55 parts by mass.
　また、（Ｄ）成分を用いる場合、（Ｄ）成分の分散性及び（Ｄ）成分と樹脂組成物中の有機成分との密着性を向上させる目的で、必要に応じ、カップリング剤を併用してもよい。該カップリング剤としては特に限定されるものではなく、例えば、シランカップリング剤又はチタネートカップリング剤を適宜選択して用いることができる。カップリング剤は１種類を単独で用いてもよく、２種類以上を併用してもよい。また、カップリング剤の使用量も特に限定されるものではなく、例えば、（Ｄ）成分１００質量部に対して０．１～５質量部としてもよく、０．５～３質量部としてもよい。この範囲であれば、諸特性の低下が少なく、上記の（Ｄ）成分の使用による特長を効果的に発揮できる傾向にある。
　なお、カップリング剤を用いる場合、樹脂組成物中に（Ｄ）成分を配合した後、カップリング剤を添加する、いわゆるインテグラルブレンド処理方式ではなく、予め無機充填材にカップリング剤を乾式又は湿式で表面処理した無機充填材を使用する方式を採用できる。この方法を採用することで、より効果的に上記（Ｄ）成分の特長を発現できる。 Further, when the component (D) is used, a coupling agent may be optionally used in combination for the purpose of improving the dispersibility of the component (D) and the adhesion between the component (D) and the organic component in the resin composition. You may. The coupling agent is not particularly limited, and for example, a silane coupling agent or a titanate coupling agent can be appropriately selected and used. One type of coupling agent may be used alone, or two or more types may be used in combination. The amount of the coupling agent used is not particularly limited, and may be, for example, 0.1 to 5 parts by mass, or 0.5 to 3 parts by mass, relative to 100 parts by mass of the component (D). . Within this range, the various characteristics are less likely to deteriorate, and the features of the use of the component (D) tend to be effectively exhibited.
When a coupling agent is used, it is not a so-called integral blend treatment method in which the coupling agent is added after the component (D) is mixed in the resin composition, and the coupling agent is previously added to the inorganic filler by a dry method or A method using a wet surface-treated inorganic filler can be adopted. By adopting this method, the features of the component (D) can be more effectively exhibited.
　本発明において（Ｄ）成分を用いる場合、（Ｄ）成分の樹脂組成物への分散性を向上させる目的で、必要に応じ、（Ｄ）成分を予め有機溶媒中に分散させたスラリーとして用いることができる。（Ｄ）成分をスラリー化する際に使用される有機溶媒は特に制限はないが、例えば、上述したポリフェニレンエーテル誘導体（Ａ）の製造工程で例示した有機溶媒が適用できる。これらは１種類を単独で用いてもよく、２種類以上を併用してもよい。またこれらの中でも、分散性の観点から、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノンを選択できる。また、スラリーの固形分（不揮発分）濃度は特に制限はないが、例えば、無機充填材（Ｄ）の沈降性及び分散性の観点から、５０～８０質量％であってもよく、６０～８０質量％であってもよい。 When the component (D) is used in the present invention, it is used as a slurry in which the component (D) is previously dispersed in an organic solvent for the purpose of improving the dispersibility of the component (D) in the resin composition. You can The organic solvent used when the component (D) is slurried is not particularly limited, but, for example, the organic solvent exemplified in the production process of the polyphenylene ether derivative (A) described above can be applied. These may be used alone or in combination of two or more. Among these, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone can be selected from the viewpoint of dispersibility. Further, the solid content (nonvolatile content) concentration of the slurry is not particularly limited, but may be 50 to 80% by mass, or 60 to 80% by mass from the viewpoint of sedimentation and dispersibility of the inorganic filler (D). It may be% by mass.
（硬化促進剤（Ｅ））
　本発明の樹脂組成物に硬化促進剤（Ｅ）を含有させることで、樹脂組成物の硬化性を向上させ、１０ＧＨｚ帯以上の高周波数帯における誘電特性、耐熱性、導体との接着性、弾性率及びガラス転移温度を向上させることができる傾向にある。
　（Ｅ）成分としては、例えば、ｐ－トルエンスルホン酸等の酸性触媒；トリエチルアミン、ピリジン、トリブチルアミン等のアミン化合物；メチルイミダゾール、フェニルイミダゾール、イソシアネートマスクイミダゾール（例えば、ヘキサメチレンジイソシアネート樹脂と２－エチル－４－メチルイミダゾールの付加反応物等）等のイミダゾール化合物；第３級アミン化合物；第４級アンモニウム化合物；トリフェニルホスフィン等のリン系化合物；ジクミルパーオキサイド、２，５－ジメチル－２，５－ビス（ｔ－ブチルパーオキシ）－３－ヘキシン、２，５－ジメチル－２，５－ビス（ｔ－ブチルパーオキシ）ヘキサン、ｔ－ブチルパーオキシイソプロピルモノカーボネート、α，α’－ビス（ｔ－ブチルパーオキシ）ジイソプロピルベンゼン等の有機過酸化物；マンガン、コバルト、亜鉛等のカルボン酸塩などが挙げられる。これらは１種類を単独で用いてもよく、２種類以上を併用してもよい。これらの中でも、耐熱性、ガラス転移温度及び保存安定性の観点から、イミダゾール化合物、有機過酸化物、カルボン酸塩であってもよく、耐熱性、ガラス転移温度、弾性率及び熱膨張係数の観点から、イミダゾール化合物と、有機過酸化物又はカルボン酸塩とを併用してもよい。また、有機過酸化物の中では、α，α’－ビス（ｔ－ブチルパーオキシ）ジイソプロピルベンゼンを選択してもよく、カルボン酸塩の中では、ナフテン酸マンガンを選択してもよい。 (Curing accelerator (E))
By containing a curing accelerator (E) in the resin composition of the present invention, the curability of the resin composition is improved, and dielectric properties, heat resistance, adhesion to conductors, elasticity in a high frequency band of 10 GHz band or higher. The rate and the glass transition temperature tend to be improved.
Examples of the component (E) include acidic catalysts such as p-toluenesulfonic acid; amine compounds such as triethylamine, pyridine and tributylamine; methylimidazole, phenylimidazole, isocyanate mask imidazole (eg, hexamethylene diisocyanate resin and 2-ethylamine). Imidazole compounds such as addition reaction products of 4-methylimidazole); tertiary amine compounds; quaternary ammonium compounds; phosphorus compounds such as triphenylphosphine; dicumyl peroxide, 2,5-dimethyl-2, 5-bis (t-butylperoxy) -3-hexyne, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, α, α′-bis (T-butylperoxy) diisopropyl ester Organic peroxides such as Zen; manganese, cobalt, etc. carboxylates of zinc, and the like. These may be used alone or in combination of two or more. Among these, from the viewpoints of heat resistance, glass transition temperature and storage stability, they may be imidazole compounds, organic peroxides and carboxylates, and heat resistance, glass transition temperature, elastic modulus and thermal expansion coefficient. Therefore, the imidazole compound and the organic peroxide or carboxylate may be used in combination. Further, among the organic peroxides, α, α′-bis (t-butylperoxy) diisopropylbenzene may be selected, and among the carboxylates, manganese naphthenate may be selected.
　本発明の樹脂組成物に（Ｅ）成分を含有させる場合、（Ｅ）成分の含有量は特に制限されるものではないが、例えば、本発明の樹脂成分の総和１００質量部に対して、０．０１～１０質量部であってもよく、０．０１～５質量部であってもよく、０．１～５質量部であってもよく、０．５～５質量部であってもよい。このような範囲で（Ｅ）成分を用いると、より良好な耐熱性及び保存安定性が得られる傾向にある。 When the component (E) is contained in the resin composition of the present invention, the content of the component (E) is not particularly limited, but is, for example, 0 with respect to 100 parts by mass of the total amount of the resin components of the present invention. 0.01 to 10 parts by mass, 0.01 to 5 parts by mass, 0.1 to 5 parts by mass, or 0.5 to 5 parts by mass. .. When the component (E) is used in such a range, better heat resistance and storage stability tend to be obtained.
（難燃剤（Ｆ））
　本発明の樹脂組成物に難燃剤（Ｆ）及び必要に応じて難燃助剤を含有させることで、樹脂組成物の難燃性を向上させることができる傾向にある。
　（Ｆ）成分としては、リン系難燃剤、金属水和物、ハロゲン系難燃剤等が挙げられる。環境問題の観点から、リン系難燃剤及び金属水和物であってもよい。難燃剤（Ｆ）は、１種類を単独で用いてもよく、２種類以上を併用してもよい。 (Flame retardant (F))
When the resin composition of the present invention contains a flame retardant (F) and, if necessary, a flame retardant aid, the flame retardancy of the resin composition tends to be improved.
Examples of the component (F) include phosphorus-based flame retardants, metal hydrates, halogen-based flame retardants, and the like. From the viewpoint of environmental problems, phosphorus-based flame retardants and metal hydrates may be used. As the flame retardant (F), one type may be used alone, or two or more types may be used in combination.
－リン系難燃剤－
　リン系難燃剤としては、一般的に難燃剤として使用されるもののうち、リン原子を含有するものであれば特に制限はなく、無機系のリン系難燃剤であってもよいし、有機系のリン系難燃剤であってもよい。なお、環境問題の観点から、ハロゲン原子を含有しないものを選択できる。１０ＧＨｚ帯以上の高周波数帯における誘電特性、導体との接着性、耐熱性、ガラス転移温度、熱膨張係数及び難燃性の観点からは、有機系のリン系難燃剤であってもよい。
　無機系のリン系難燃剤としては、例えば、赤リン；リン酸一アンモニウム、リン酸二アンモニウム、リン酸三アンモニウム、ポリリン酸アンモニウム等のリン酸アンモニウム；リン酸アミド等の無機系含窒素リン化合物；リン酸；ホスフィンオキシドなどが挙げられる。
　有機系のリン系難燃剤としては、例えば、芳香族リン酸エステル、１置換ホスホン酸ジエステル、２置換ホスフィン酸エステル、２置換ホスフィン酸の金属塩、有機系含窒素リン化合物、環状有機リン化合物等が挙げられる。これらの中でも、芳香族リン酸エステル化合物、２置換ホスフィン酸の金属塩を選択できる。ここで、金属塩としては、リチウム塩、ナトリウム塩、カリウム塩、カルシウム塩、マグネシウム塩、アルミニウム塩、チタン塩、亜鉛塩のいずれかであってもよく、アルミニウム塩であってもよい。また、有機系のリン系難燃剤の中では、芳香族リン酸エステルを選択できる。 -Phosphorus flame retardant-
The phosphorus-based flame retardant is not particularly limited as long as it contains a phosphorus atom among those generally used as a flame retardant, and may be an inorganic phosphorus-based flame retardant or an organic-based flame retardant. It may be a phosphorus-based flame retardant. From the viewpoint of environmental issues, it is possible to select one that does not contain a halogen atom. From the viewpoint of dielectric properties in a high frequency band of 10 GHz band or higher, adhesiveness with a conductor, heat resistance, glass transition temperature, coefficient of thermal expansion and flame retardancy, an organic phosphorus-based flame retardant may be used.
Examples of inorganic phosphorus-based flame retardants include red phosphorus; ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate; inorganic nitrogen-containing phosphorus compounds such as phosphoramide. Phosphoric acid; phosphine oxide and the like.
Examples of the organic phosphorus flame retardant include aromatic phosphoric acid ester, 1-substituted phosphonic acid diester, 2-substituted phosphinic acid ester, 2-substituted phosphinic acid metal salt, organic nitrogen-containing phosphorus compound, cyclic organic phosphorus compound, and the like. Is mentioned. Among these, aromatic phosphoric acid ester compounds and metal salts of disubstituted phosphinic acids can be selected. Here, the metal salt may be any one of a lithium salt, a sodium salt, a potassium salt, a calcium salt, a magnesium salt, an aluminum salt, a titanium salt and a zinc salt, or may be an aluminum salt. Further, among the organic phosphorus-based flame retardants, aromatic phosphate ester can be selected.
　芳香族リン酸エステルとしては、例えば、トリフェニルホスフェート、トリクレジルホスフェート、トリキシレニルホスフェート、クレジルジフェニルホスフェート、クレジルジ－２，６－キシレニルホスフェート、レゾルシノールビス（ジフェニルホスフェート）、１，３－フェニレンビス（ジ－２，６－キシレニルホスフェート）、ビスフェノールＡ－ビス（ジフェニルホスフェート）、１，３－フェニレンビス（ジフェニルホスフェート）等が挙げられる。
　１置換ホスホン酸ジエステルとしては、例えば、フェニルホスホン酸ジビニル、フェニルホスホン酸ジアリル、フェニルホスホン酸ビス（１－ブテニル）等が挙げられる。
　２置換ホスフィン酸エステルとしては、例えば、ジフェニルホスフィン酸フェニル、ジフェニルホスフィン酸メチル等が挙げられる。
　２置換ホスフィン酸の金属塩としては、ジアルキルホスフィン酸の金属塩、ジアリルホスフィン酸の金属塩、ジビニルホスフィン酸の金属塩、ジアリールホスフィン酸の金属塩等が挙げられる。これら金属塩は、リチウム塩、ナトリウム塩、カリウム塩、カルシウム塩、マグネシウム塩、アルミニウム塩、チタン塩、亜鉛塩のいずれかであってもよく、アルミニウム塩を選択してもよい。
　有機系含窒素リン化合物としては、例えば、ビス（２－アリルフェノキシ）ホスファゼン、ジクレジルホスファゼン等のホスファゼン化合物；リン酸メラミン；ピロリン酸メラミン；ポリリン酸メラミン；ポリリン酸メラムなどが挙げられる。
　環状有機リン化合物としては、９，１０－ジヒドロ－９－オキサ－１０－ホスファフェナントレン－１０－オキシド、１０－（２，５－ジヒドロキシフェニル）－９，１０－ジヒドロ－９－オキサ－１０－ホスファフェナントレン－１０－オキシド等が挙げられる。
　これらの中でも、芳香族リン酸エステル、２置換ホスフィン酸の金属塩及び環状有機リン化合物から選択される少なくとも１種類であってもよく、２置換ホスフィン酸の金属塩及び環状有機リン化合物から選択される少なくとも１種類であってもよく、２置換ホスフィン酸の金属塩及び環状有機リン化合物を併用してもよい。特に、２置換ホスフィン酸の金属塩としては、ジアルキルホスフィン酸の金属塩であってもよく、ジアルキルホスフィン酸のアルミニウム塩であってもよい。環状有機リン化合物としては、１０－（２，５－ジヒドロキシフェニル）－９，１０－ジヒドロ－９－オキサ－１０－ホスファフェナントレン－１０－オキシドであってもよい。 Examples of the aromatic phosphoric acid ester include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl di-2,6-xylenyl phosphate, resorcinol bis (diphenyl phosphate), 1,3 -Phenylene bis (di-2,6-xylenyl phosphate), bisphenol A-bis (diphenyl phosphate), 1,3-phenylene bis (diphenyl phosphate), etc. may be mentioned.
Examples of mono-substituted phosphonic acid diesters include divinyl phenylphosphonate, diallyl phenylphosphonate, and bis (1-butenyl) phenylphosphonate.
Examples of the 2-substituted phosphinic acid ester include phenyl diphenylphosphinate and methyl diphenylphosphinate.
Examples of the metal salt of disubstituted phosphinic acid include a metal salt of dialkylphosphinic acid, a metal salt of diallylphosphinic acid, a metal salt of divinylphosphinic acid, a metal salt of diarylphosphinic acid, and the like. These metal salts may be any of lithium salt, sodium salt, potassium salt, calcium salt, magnesium salt, aluminum salt, titanium salt and zinc salt, and aluminum salt may be selected.
Examples of the organic nitrogen-containing phosphorus compounds include phosphazene compounds such as bis (2-allylphenoxy) phosphazene and dicresylphosphazene; melamine phosphate; melamine pyrophosphate; melamine polyphosphate; melam polyphosphate.
Examples of the cyclic organic phosphorus compound include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-10- Examples thereof include phosphaphenanthrene-10-oxide.
Among these, at least one kind selected from an aromatic phosphoric acid ester, a metal salt of a substituted phosphinic acid and a cyclic organic phosphorus compound may be used, and it may be selected from a metal salt of a substituted phosphinic acid and a cyclic organic phosphorus compound. At least one kind thereof may be used, and a metal salt of a disubstituted phosphinic acid and a cyclic organic phosphorus compound may be used in combination. In particular, the metal salt of disubstituted phosphinic acid may be a metal salt of dialkylphosphinic acid or an aluminum salt of dialkylphosphinic acid. The cyclic organophosphorus compound may be 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.
　また、前記芳香族リン酸エステルは、下記一般式（Ｆ－１）で表される芳香族リン酸エステルであってもよく、前記２置換ホスフィン酸の金属塩は、下記一般式（Ｆ－２）で表される２置換ホスフィン酸の金属塩であってもよい。
Figure JPOXMLDOC01-appb-C000035
 Further, the aromatic phosphate ester may be an aromatic phosphate ester represented by the following general formula (F-1), and the metal salt of the disubstituted phosphinic acid may be represented by the following general formula (F-2). A metal salt of a disubstituted phosphinic acid represented by
Figure JPOXMLDOC01-appb-C000035
（式中、ＲＦ１～ＲＦ３は各々独立に、炭素数１～５の脂肪族炭化水素基又はハロゲン原子である。ｆ１及びｆ２は各々独立に０～５の整数であり、ｆ３は０～４の整数である。
　ＲＦ４及びＲＦ５は各々独立に、炭素数１～５の脂肪族炭化水素基又は炭素数６～１４の芳香族炭化水素基である。Ｍは、リチウム原子、ナトリウム原子、カリウム原子、カルシウム原子、マグネシウム原子、アルミニウム原子、チタン原子、亜鉛原子である。ｙは、１～４の整数である。） (In the formula, R F1 to R F3 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. F1 and f2 are each independently an integer of 0 to 5, and f3 is 0 to It is an integer of 4.
R F4 and R F5 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms. M is 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 is an integer of 1 to 4. )
　ＲＦ１～ＲＦ３が表す炭素数１～５の脂肪族炭化水素基及びハロゲン原子としては、前記一般式（Ｉ）中のＲａ１１の場合と同じものが挙げられる。
　ｆ１及びｆ２はいずれも、０～２の整数であってもよく、２であってもよい。ｆ３は０～２の整数であってもよく、０又は１であってもよく、０であってもよい。
　ＲＦ４及びＲＦ５が表す炭素数１～５の脂肪族炭化水素基としては、該脂肪族炭化水素基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔ－ブチル基、ｎ－ペンチル基等が挙げられる。該脂肪族炭化水素基としては、炭素数１～３の脂肪族炭化水素基であってもよく、エチル基であってもよい。
　ＲＦ４及びＲＦ５が表す炭素数６～１４の芳香族炭化水素基としては、例えば、フェニル基、ナフチル基、ビフェニリル基、アントリル基等が挙げられる。該芳香族炭化水素基としては、炭素数６～１０の芳香族炭化水素基であってもよい。
　ｙは金属イオンの価数を表しており、つまり、Ｍの種類に対応して１～４の範囲内で変化する。
　Ｍとしては、アルミニウム原子であってもよい。なお、Ｍがアルミニウム原子である場合、ｙは３である。 As the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R F1 to R F3 , the same ones as in the case of R a11 in the general formula (I) can be mentioned.
Both f1 and f2 may be an integer of 0 to 2 or 2. f3 may be an integer of 0 to 2, may be 0 or 1, and may be 0.
The aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R F4 and R F5 is, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group or an n-butyl group. , Isobutyl group, t-butyl group, n-pentyl group and the like. The aliphatic hydrocarbon group may be an aliphatic hydrocarbon group having 1 to 3 carbon atoms or an ethyl group.
Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms represented by R F4 and R F5 include a phenyl group, a naphthyl group, a biphenylyl group and an anthryl group. The aromatic hydrocarbon group may be an aromatic hydrocarbon group having 6 to 10 carbon atoms.
y represents the valence of the metal ion, that is, it changes within the range of 1 to 4 corresponding to the type of M.
M may be an aluminum atom. In addition, when M is an aluminum atom, y is 3.
－金属水和物－
　金属水和物としては、例えば、水酸化アルミニウムの水和物、水酸化マグネシウムの水和物等が挙げられる。これらは１種類を単独で用いてもよく、２種類以上を併用してもよい。該金属水酸化物は無機充填材にも該当し得るが、難燃性を付与し得る材料の場合には難燃剤に分類する。 -Metal hydrate-
Examples of metal hydrates include aluminum hydroxide hydrate and magnesium hydroxide hydrate. These may be used alone or in combination of two or more. The metal hydroxide may be an inorganic filler, but a material capable of imparting flame retardancy is classified as a flame retardant.
－ハロゲン系難燃剤－
　ハロゲン系難燃剤としては、塩素系難燃剤、臭素系難燃剤等が挙げられる。塩素系難燃剤としては、例えば、塩素化パラフィン等が挙げられる。臭素系難燃剤としては、例えば、臭素化ビスフェノールＡ型エポキシ樹脂、臭素化フェノールノボラック型エポキシ樹脂等の臭素化エポキシ樹脂；ヘキサブロモベンゼン、ペンタブロモトルエン、エチレンビス（ペンタブロモフェニル）、エチレンビステトラブロモフタルイミド、１，２－ジブロモ－４－（１，２－ジブロモエチル）シクロヘキサン、テトラブロモシクロオクタン、ヘキサブロモシクロドデカン、ビス（トリブロモフェノキシ）エタン、臭素化ポリフェニレンエーテル、臭素化ポリスチレン、２，４，６－トリス（トリブロモフェノキシ）－１，３，５－トリアジン等の臭素化添加型難燃剤（ここで、「添加型」とは、臭素が化学的に結合していない形態でポリマーに導入された、つまりブレンドされたものをいう。）；トリブロモフェニルマレイミド、トリブロモフェニルアクリレート、トリブロモフェニルメタクリレート、テトラブロモビスフェノールＡ型ジメタクリレート、ペンタブロモベンジルアクリレート、臭素化スチレン等の不飽和二重結合基含有の臭素化反応型難燃剤（ここで、「反応型」とは、化学的に結合した形態でポリマーに臭素が導入されたものをいう。）などが挙げられる。これらは１種類を単独で使用してもよいし、２種類以上を併用してもよい。 -Halogen flame retardant-
Examples of halogen-based flame retardants include chlorine-based flame retardants and bromine-based flame retardants. Examples of the chlorine-based flame retardant include chlorinated paraffin and the like. Examples of the brominated flame retardant include brominated epoxy resins such as brominated bisphenol A type epoxy resin and brominated phenol novolac type epoxy resin; hexabromobenzene, pentabromotoluene, ethylenebis (pentabromophenyl), ethylenebistetra Bromophthalimide, 1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis (tribromophenoxy) ethane, brominated polyphenylene ether, brominated polystyrene, 2, Brominated addition type flame retardants such as 4,6-tris (tribromophenoxy) -1,3,5-triazine (here, “addition type” means that bromine is not chemically bonded to the polymer. Introduced, that is, blended.); Bromination reaction type flame retardants containing unsaturated double bond groups such as bromophenyl maleimide, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromobisphenol A type dimethacrylate, pentabromobenzyl acrylate, brominated styrene (here, The “reactive type” refers to a polymer in which bromine is introduced in a chemically bonded form) and the like. These may be used alone or in combination of two or more.
（（Ｆ）成分の含有量）
　本発明の樹脂組成物が（Ｆ）成分を含有する場合、（Ｆ）成分としてリン系難燃剤を用いるときは、樹脂組成物中のリン系難燃剤の含有量は特に制限されるものではないが、例えば、樹脂成分の総和１００質量部に対して、リン原子換算で、０．２～５質量部であることが好ましく、０．３～３質量部であることがより好ましく、０．５～３質量部であることがさらに好ましい。リン原子の含有量が０．２質量部以上の場合、より良好な難燃性が得られる傾向にある。また、リン原子の含有量が５質量部以下である場合、より良好な成形性、導体との高接着性、優れた耐熱性及び高ガラス転移温度が得られる傾向にある。
　一方、本発明の樹脂組成物にハロゲン系難燃剤を含有させる場合、環境問題及び耐薬品性の観点から、樹脂成分の総和１００質量部に対して、２０質量部以下であることが好ましく、１０質量部以下であることがより好ましく、５質量部以下であることがさらに好ましく、３質量部以下であることが特に好ましい。（Ｆ）成分としては、ハロゲン系難燃剤を使用しない態様も好ましい。
　また、本発明の樹脂組成物にリン系難燃剤以外の難燃剤を含有させる場合、特に制限されるものではないが、樹脂成分の総和１００質量部に対して、０．５～２０質量部であってもよく、１～１５質量部であってもよく、１～１０質量部であってもよく、２～８質量部であってもよい。 (Content of component (F))
When the resin composition of the present invention contains the component (F), when the phosphorus-based flame retardant is used as the component (F), the content of the phosphorus-based flame retardant in the resin composition is not particularly limited. Is preferably 0.2 to 5 parts by mass, more preferably 0.3 to 3 parts by mass, and more preferably 0.5 to 5 parts by mass in terms of phosphorus atom, based on 100 parts by mass of the total resin components. It is more preferably about 3 to 3 parts by mass. When the phosphorus atom content is 0.2 parts by mass or more, better flame retardancy tends to be obtained. Further, when the content of phosphorus atoms is 5 parts by mass or less, better moldability, high adhesiveness with a conductor, excellent heat resistance, and high glass transition temperature tend to be obtained.
On the other hand, when the resin composition of the present invention contains a halogen-based flame retardant, it is preferably 20 parts by mass or less based on 100 parts by mass of the total resin components from the viewpoint of environmental problems and chemical resistance. It is more preferably not more than 5 parts by mass, further preferably not more than 5 parts by mass, particularly preferably not more than 3 parts by mass. As the component (F), a mode in which a halogen-based flame retardant is not used is also preferable.
When the resin composition of the present invention contains a flame retardant other than the phosphorus-based flame retardant, it is not particularly limited, but is 0.5 to 20 parts by mass relative to 100 parts by mass of the total resin components. The amount may be 1 to 15 parts by mass, 1 to 10 parts by mass, or 2 to 8 parts by mass.
（難燃助剤）
　本発明の樹脂組成物には、難燃助剤、例えば、三酸化アンチモン、モリブデン酸亜鉛等の無機系難燃助剤を含有させることができる。
　本発明の樹脂組成物に難燃助剤を含有させる場合、その含有量は特に制限されるものではないが、例えば、樹脂成分の総和１００質量部に対して、０．１～２０質量部であってもよく、０．１～１０質量部であってもよい。このような範囲で難燃助剤を用いると、より良好な耐薬品性が得られる傾向にある。 (Flame retardant aid)
The resin composition of the present invention may contain a flame retardant aid, for example, an inorganic flame retardant aid such as antimony trioxide or zinc molybdate.
When the flame retardant aid is contained in the resin composition of the present invention, its content is not particularly limited, but for example, it is 0.1 to 20 parts by mass with respect to 100 parts by mass of the total resin components. The amount may be 0.1 to 10 parts by mass. When the flame retardant aid is used in such a range, better chemical resistance tends to be obtained.
（架橋剤（Ｇ））
　本発明の樹脂組成物に架橋剤（Ｇ）を含有させることで、（Ａ）成分と（Ｂ）成分との反応を促進することができる傾向にある。
　架橋剤（Ｇ）としては、（Ａ）成分及び（Ｂ）成分と架橋反応し得るものであれば特に制限されるものではないが、マレイミド基が有する炭素－炭素二重結合と反応し得る基を有する化合物であることが好ましい。その中でも、架橋剤（Ｇ）としては、エチレン性不飽和結合を２個以上有する架橋剤であることが好ましい。前記エチレン性不飽和結合としては、例えば、ビニル基、イソプロペニル基、アリル基、１－メチルアリル基、３－ブテニル基等の不飽和脂肪族炭化水素基；マレイミド基、（メタ）アクリロイル基等のヘテロ原子を含む置換基などに含まれる不飽和結合が挙げられる。架橋剤（Ｇ）としては、１０ＧＨｚ帯以上の高周波数帯における誘電特性の観点から、エチレン性不飽和結合を上記不飽和脂肪族炭化水素基として有するものが好ましく、ビニル基として有するものがより好ましい。架橋剤（Ｇ）が１分子中に有するエチレン性不飽和結合の数は、優れた耐熱性を得る観点から、好ましくは３個以上、より好ましくは５個以上、さらに好ましくは１０個以上である。 (Crosslinking agent (G))
By incorporating the crosslinking agent (G) into the resin composition of the present invention, the reaction between the component (A) and the component (B) tends to be promoted.
The cross-linking agent (G) is not particularly limited as long as it can cross-link with the components (A) and (B), but it is a group capable of reacting with the carbon-carbon double bond of the maleimide group. It is preferable that the compound has Among them, the crosslinking agent (G) is preferably a crosslinking agent having two or more ethylenically unsaturated bonds. Examples of the ethylenically unsaturated bond include unsaturated aliphatic hydrocarbon groups such as vinyl group, isopropenyl group, allyl group, 1-methylallyl group and 3-butenyl group; maleimide group, (meth) acryloyl group and the like. An unsaturated bond contained in a substituent containing a hetero atom and the like can be mentioned. As the cross-linking agent (G), those having an ethylenic unsaturated bond as the unsaturated aliphatic hydrocarbon group are preferable, and those having a vinyl group are more preferable, from the viewpoint of dielectric properties in a high frequency band of 10 GHz or higher. . The number of ethylenically unsaturated bonds that the cross-linking agent (G) has in one molecule is preferably 3 or more, more preferably 5 or more, and further preferably 10 or more from the viewpoint of obtaining excellent heat resistance. .
　架橋剤（Ｇ）としては、具体的には、不飽和ポリエステル；側鎖に炭素－炭素二重結合を有するポリブタジエン、側鎖に炭素－炭素二重結合を有するポリイソプレン等の、側鎖に炭素－炭素二重結合を有するポリアルカジエン；ジビニルベンゼン、ジビニルビフェニル等のポリビニル化合物；ポリ（メタ）アクリレート化合物；トリアリルシアヌレート、トリアリルイソシアヌレート等のポリアリル化合物；ジアミノジフェニルメタン等のポリアミン化合物などが挙げられる。これらの中でも、側鎖に炭素－炭素二重結合を有するポリアルカジエンが好ましく、側鎖に炭素－炭素二重結合を有するポリブタジエンがより好ましい。架橋剤は、１種類を単独で使用してもよいし、２種類以上を併用してもよい。 Specific examples of the cross-linking agent (G) include unsaturated polyester; polybutadiene having a carbon-carbon double bond in its side chain, carbon in its side chain such as polyisoprene having a carbon-carbon double bond in its side chain. A polyalkadiene having a carbon double bond; a polyvinyl compound such as divinylbenzene and divinylbiphenyl; a poly (meth) acrylate compound; a polyallyl compound such as triallyl cyanurate and triallyl isocyanurate; a polyamine compound such as diaminodiphenylmethane Can be mentioned. Among these, polyalkadienes having a carbon-carbon double bond in the side chain are preferable, and polybutadiene having a carbon-carbon double bond in the side chain is more preferable. As the crosslinking agent, one type may be used alone, or two or more types may be used in combination.
　本発明の樹脂組成物には、さらに必要に応じて、熱可塑性樹脂、エラストマー等の樹脂材料（前記（Ｃ）成分を除く）、並びに、カップリング剤、酸化防止剤、熱安定剤、帯電防止剤、紫外線吸収剤、顔料、着色剤、滑剤等を適宜選択して含有させることができる。これらは１種類を単独で使用してもよく、２種類以上を併用してもよい。また、これらの使用量は特に限定されるものではなく、本発明の効果を阻害しない範囲で使用すればよい。 The resin composition of the present invention may further contain a resin material such as a thermoplastic resin and an elastomer (excluding the component (C)), a coupling agent, an antioxidant, a heat stabilizer, and an antistatic agent, if necessary. Agents, ultraviolet absorbers, pigments, colorants, lubricants and the like can be appropriately selected and contained. These may be used alone or in combination of two or more. Further, the amount of these used is not particularly limited, and may be used within a range that does not impair the effects of the present invention.
（有機溶剤）
　本発明の樹脂組成物は、希釈することによって取り扱いを容易にするという観点及び後述するプリプレグを製造し易くする観点から、有機溶剤を含有させてもよい。有機溶剤を含有させた樹脂組成物は、一般的に、樹脂ワニス又はワニスと称されることがある。
　該有機溶剤としては、特に制限されないが、例えば、エタノール、プロパノール、ブタノール、メチルセロソルブ、ブチルセロソルブ、プロピレングリコールモノメチルエーテル等のアルコール系溶剤；アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶剤；テトラヒドロフラン等のエーテル系溶剤；トルエン、キシレン、メシチレン等の芳香族系溶剤；ジメチルホルムアミド、ジメチルアセトアミド、Ｎ－メチルピロリドン等の窒素原子含有溶剤；ジメチルスルホキシド等の硫黄原子含有溶剤；γ－ブチロラクトン等のエステル系溶剤などが挙げられる。
　これらの中でも、溶解性の観点から、アルコール系溶剤、ケトン系溶剤、窒素原子含有溶剤であってもよく、ケトン系溶剤であってもよく、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノンであってもよく、メチルエチルケトンであってもよい。
　有機溶剤は、１種類を単独で用いてもよく、２種類以上を併用してもよい。 (Organic solvent)
The resin composition of the present invention may contain an organic solvent from the viewpoint of facilitating the handling by diluting and facilitating the production of a prepreg described later. The resin composition containing an organic solvent is generally referred to as a resin varnish or a varnish.
The organic solvent is not particularly limited, but examples thereof include alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve and propylene glycol monomethyl ether; ketone type solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; tetrahydrofuran. Ether solvent such as; aromatic solvent such as toluene, xylene, mesitylene; nitrogen atom-containing solvent such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone; sulfur atom-containing solvent such as dimethyl sulfoxide; ester such as γ-butyrolactone Examples include system solvents.
Among these, from the viewpoint of solubility, alcohol-based solvent, ketone-based solvent, may be a nitrogen atom-containing solvent, may be a ketone-based solvent, acetone, methyl ethyl ketone, methyl isobutyl ketone, even cyclohexanone Well, it may be methyl ethyl ketone.
As the organic solvent, one type may be used alone, or two or more types may be used in combination.
　本発明の樹脂組成物における有機溶剤の含有量は、特に制限はないが、固形分濃度が３０～９０質量％であってもよいし、４０～８０質量％であってもよく、４０～７０質量％であってもよく、４０～６０質量％であってもよい。固形分濃度が上記の範囲内である樹脂組成物を用いることで、取り扱い性が容易となり、さらに基材への含浸性及び製造されるプリプレグの外観が良好で、後述するプリプレグ中の樹脂の固形分濃度の調整が容易となり、所望の厚みとなるようなプリプレグの製造がより容易となる傾向にある。 The content of the organic solvent in the resin composition of the present invention is not particularly limited, but the solid content concentration may be 30 to 90% by mass, 40 to 80% by mass, or 40 to 70% by mass. It may be mass% or may be 40 to 60 mass%. By using a resin composition having a solid content concentration within the above range, the handling becomes easy, the impregnation into the substrate and the appearance of the prepreg produced are good, and the solid content of the resin in the prepreg described below. It tends to be easier to adjust the concentration, and it becomes easier to manufacture a prepreg having a desired thickness.
　前記（Ａ）及び（Ｂ）成分、必要に応じて併用されるその他の成分、及び必要に応じて有機溶媒を公知の方法で混合し、本発明の樹脂組成物を得ることができる。この際、撹拌しながら溶解又は分散させてもよい。混合順序、温度、時間等の条件は、特に限定されず任意に設定することができる。 The resin composition of the present invention can be obtained by mixing the above-mentioned components (A) and (B), other components used in combination if necessary, and, if necessary, an organic solvent by a known method. At this time, it may be dissolved or dispersed while stirring. Conditions such as mixing order, temperature, time, etc. are not particularly limited and can be set arbitrarily.
　本発明の樹脂組成物は相容性が良好であり、１日放置しても析出物は生じない傾向にある。また、より相容性が優れた態様においては、１週間放置しても析出物が生じない（但し、相分離することはある。）傾向にあり、さらに相容性が優れた態様においては、１週間放置しても、相分離さえしない傾向にある。
　本発明の樹脂組成物の硬化物（ガラスクロス等の繊維基材を含まない積層体及び樹脂フィルム）は、１０ＧＨｚにおける誘電率（Ｄｋ）が２．９０以下となる傾向にあり、より好ましいものでは２．８０以下、さらに好ましいものでは２．７５以下となる傾向にある。また、１０ＧＨｚにおける誘電正接（Ｄｆ）は、０．００５５以下となる傾向にある。
　１０ＧＨｚにおける誘電率（Ｄｋ）の下限値に特に制限はないが、２．４以上となる傾向にあり、２．６以上であってもよい。
　また、１０ＧＨｚにおける誘電正接（Ｄｆ）の下限値に特に制限はないが、０．００１５以上となる傾向にあり、０．００２０以上であってもよく、０．００２３以上であってもよい。
　より好ましい態様では、１０ＧＨｚにおける誘電正接（Ｄｆ）は０．００５０以下であり、０．００４５以下であり、０．００３５以下であり、０．００３０以下であり、０．００２９以下である。近年、１０ＧＨｚにおける誘電正接（Ｄｆ）については改善が厳しく要求されつつあり、０．００３０以下となる場合は極めて好ましく、達成することが非常に難しい水準である。
　なお、誘電率及び誘電正接は、空洞共振器法により測定した値であり、より詳細には、実施例に記載する方法によって測定された値である。また、単に誘電率というとき、比誘電率を意味する。 The resin composition of the present invention has good compatibility, and there is a tendency that precipitates do not occur even if left for one day. Further, in a more excellent compatibility mode, there is a tendency that precipitates do not occur even if left for one week (however, phase separation may occur), and in a more excellent compatibility mode, Even if left for one week, there is a tendency that even phase separation does not occur.
The cured product of the resin composition of the present invention (a laminate and a resin film that does not include a fiber base material such as glass cloth) tends to have a dielectric constant (Dk) of 2.90 or less at 10 GHz, and more preferable one is 2.80 or less, and more preferably 2.75 or less. Moreover, the dielectric loss tangent (Df) at 10 GHz tends to be 0.0055 or less.
The lower limit of the dielectric constant (Dk) at 10 GHz is not particularly limited, but tends to be 2.4 or more, and may be 2.6 or more.
The lower limit of the dielectric loss tangent (Df) at 10 GHz is not particularly limited, but tends to be 0.0015 or more, and may be 0.0020 or more, or 0.0023 or more.
In a more preferred embodiment, the dielectric loss tangent (Df) at 10 GHz is 0.0050 or less, 0.0045 or less, 0.0035 or less, 0.0030 or less, and 0.0029 or less. In recent years, the dielectric loss tangent (Df) at 10 GHz is being severely demanded to be improved, and it is extremely preferable that the dielectric loss tangent (Df) is 0.0030 or less, which is extremely difficult to achieve.
The dielectric constant and the dielectric loss tangent are values measured by the cavity resonator method, and more specifically, values measured by the method described in Examples. Further, when simply referred to as a dielectric constant, it means a relative dielectric constant.
［プリプレグ］
　本発明は、本発明の樹脂組成物を含有してなるプリプレグも提供する。該プリプレグは、より詳細には本発明の樹脂組成物とシート状繊維補強基材とを含有してなるものであり、本発明の樹脂組成物をシート状繊維補強基材に含浸又は塗工し、次いで乾燥させることによって製造することができる。より具体的には、例えば、乾燥炉中で通常、８０～２００℃の温度で、１～３０分間加熱乾燥し、半硬化（Ｂステージ化）させることにより本発明のプリプレグを製造することができる。樹脂組成物の使用量は、乾燥後のプリプレグ中の樹脂組成物由来の固形分濃度が好ましくは３０～９０質量％、より好ましくは５０～９０質量％、さらに好ましくは６５～８０質量％となるように決定することができる。固形分濃度を上記の範囲とすることで積層板とした際、より良好な成形性が得られる傾向にある。 [Prepreg]
The present invention also provides a prepreg containing the resin composition of the present invention. More specifically, the prepreg comprises the resin composition of the present invention and a sheet-shaped fiber reinforced substrate, and the sheet-shaped fiber reinforced substrate is impregnated or coated with the resin composition of the present invention. Then, it can be manufactured by drying. More specifically, for example, the prepreg of the present invention can be produced by heating and drying in a drying oven at a temperature of usually 80 to 200 ° C. for 1 to 30 minutes and semi-curing (B-stage). . The amount of the resin composition used is such that the solid content concentration derived from the resin composition in the prepreg after drying is preferably 30 to 90% by mass, more preferably 50 to 90% by mass, and further preferably 65 to 80% by mass. Can be determined. When the solid content concentration is within the above range, a better moldability tends to be obtained when the laminate is used.
　プリプレグのシート状繊維補強基材としては、各種の電気絶縁材料用積層板に用いられている公知のものが用いられる。シート状補強基材の材質としては、Ｅガラス、Ｄガラス、Ｓガラス、Ｑガラス等の無機物繊維；ポリイミド、ポリエステル、テトラフルオロエチレン等の有機繊維；これらの混合物などが挙げられる。これらのシート状補強基材は、例えば、織布、不織布、ロービンク、チョップドストランドマット、サーフェシングマット等の形状を有する。また、シート状繊維補強基材の厚みは特に制限されず、例えば、０．０２～０．５ｍｍのものを用いることができる。また、樹脂組成物の含浸性、積層板とした際の耐熱性、耐吸湿性、及び加工性の観点から、カップリング剤等で表面処理したもの、及び機械的に開繊処理を施したものを使用できる。 As the sheet-shaped fiber-reinforced base material of the prepreg, known materials used for various laminated plates for electrical insulating materials are used. Examples of the material of the sheet-like reinforcing base material include inorganic fibers such as E glass, D glass, S glass, and Q glass; organic fibers such as polyimide, polyester, and tetrafluoroethylene; and a mixture thereof. These sheet-like reinforcing base materials have, for example, woven cloth, non-woven cloth, robink, chopped strand mat, surfacing mat and the like. Further, the thickness of the sheet-shaped fiber-reinforced base material is not particularly limited, and for example, one having a thickness of 0.02 to 0.5 mm can be used. Further, from the viewpoints of impregnation of the resin composition, heat resistance when formed into a laminated plate, moisture absorption resistance, and processability, those surface-treated with a coupling agent or the like, and those mechanically opened. Can be used.
　樹脂組成物をシート状補強基材に含浸又は塗工させる方法としては、次のホットメルト法又はソルベント法を採用できる。
　ホットメルト法は、樹脂組成物に有機溶剤を含有させず、（１）該樹脂組成物との剥離性の良い塗工紙に一旦コーティングし、それをシート状補強基材にラミネートする方法、又は（２）ダイコーターによりシート状補強基材に直接塗工する方法である。
　一方、ソルベント法は、樹脂組成物に有機溶剤を含有させ、得られた樹脂組成物にシート状補強基材を浸漬して、樹脂組成物をシート状補強基材に含浸させ、その後、乾燥させる方法である。 As a method for impregnating or coating the resin composition on the sheet-shaped reinforcing base material, the following hot melt method or solvent method can be adopted.
The hot melt method is a method in which an organic solvent is not contained in a resin composition, and (1) a coated paper having good releasability from the resin composition is once coated and laminated on a sheet-like reinforcing base material, or (2) A method in which a sheet-shaped reinforcing base material is directly coated with a die coater.
On the other hand, in the solvent method, the resin composition is allowed to contain an organic solvent, the sheet-shaped reinforcing base material is immersed in the obtained resin composition, the sheet-shaped reinforcing base material is impregnated, and then dried. Is the way.
［樹脂フィルム］
　本発明は、本発明の樹脂組成物を含有してなる樹脂フィルムも提供する。例えば、有機溶媒を含有する樹脂組成物、つまり樹脂ワニスを支持体へ塗布し、加熱乾燥させることによって、該樹脂フィルムを製造することができる。支持体としては、例えば、ポリエチレン、ポリプロピレン、ポリ塩化ビニル等のポリオレフィンのフィルム；ポリエチレンテレフタレート（以下、「ＰＥＴ」ともいう）、ポリエチレンナフタレート等のポリエステルのフィルム；ポリカーボネートフィルム、ポリイミドフィルム等の各種プラスチックフィルムなどが挙げられる。また、支持体として、銅箔、アルミニウム箔等の金属箔、離型紙などを使用してもよい。支持体には、マット処理、コロナ処理等の表面処理が施してあってもよい。また、支持体には、シリコーン樹脂系離型剤、アルキッド樹脂系離型剤、フッ素樹脂系離型剤等による離型処理が施してあってもよい。
　支持体の厚さは、特に限定されないが、１０～１５０μｍが好ましく、２５～５０μｍがより好ましい。 [Resin film]
The present invention also provides a resin film containing the resin composition of the present invention. For example, the resin film can be produced by applying a resin composition containing an organic solvent, that is, a resin varnish to a support and heating and drying. Examples of the support include polyolefin films such as polyethylene, polypropylene and polyvinyl chloride; polyester films such as polyethylene terephthalate (hereinafter also referred to as “PET”) and polyethylene naphthalate; various plastics such as polycarbonate films and polyimide films. Examples include films. Further, as the support, a metal foil such as a copper foil or an aluminum foil, a release paper, etc. may be used. The support may be subjected to surface treatment such as matte treatment and corona treatment. Further, the support may be subjected to a release treatment with a silicone resin-based release agent, an alkyd resin-based release agent, a fluororesin-based release agent, or the like.
The thickness of the support is not particularly limited, but is preferably 10 to 150 μm, more preferably 25 to 50 μm.
　支持体に樹脂ワニスを塗布する方法に特に制限はなく、例えば、コンマコーター、バーコーター、キスコーター、ロールコーター、グラビアコーター、ダイコーター等の当業者に公知の塗工装置を用いることができる。これらの塗工装置は、膜厚によって、適宜選択すればよい。
　乾燥温度及び乾燥時間は、有機溶媒の使用量、及び使用する有機溶媒の沸点等に応じて適宜決定すればよいが、例えば、４０～６０質量％程度の有機溶媒を含む樹脂ワニスの場合、５０～１５０℃で３～１０分程度乾燥させることにより、樹脂フィルムを好適に形成することができる。 The method of applying the resin varnish to the support is not particularly limited, and for example, a coating device known to those skilled in the art such as a comma coater, a bar coater, a kiss coater, a roll coater, a gravure coater, or a die coater can be used. These coating devices may be appropriately selected depending on the film thickness.
The drying temperature and the drying time may be appropriately determined according to the amount of the organic solvent used, the boiling point of the organic solvent used, and the like. For example, in the case of a resin varnish containing about 40 to 60 mass% of the organic solvent, 50 The resin film can be suitably formed by drying at about 150 ° C. for about 3 to 10 minutes.
［積層板］
　本発明のプリプレグと金属箔とを含有してなる積層板を製造することもできる。具体的には、本発明のプリプレグ１枚の片面もしくは両面に金属箔を配置するか、又は本発明のプリプレグ２枚以上を重ねて得られるプリプレグの片面もしくは両面に金属箔を配置し、次いで加熱加圧成形することによって積層板を得ることができる。金属箔が配置された積層板は、金属張り積層板と称されることもある。
　金属箔の金属としては、電気絶縁材料用途で用いられるものであれば特に制限されないが、導電性の観点から、銅、金、銀、ニッケル、白金、モリブデン、ルテニウム、アルミニウム、タングステン、鉄、チタン、クロム、又はこれらの金属元素のうちの少なくとも１種類を含む合金であってもよく、銅、アルミニウムであってもよく、銅であることが好ましい。
　加熱加圧成形の条件は特に制限されるものではないが、例えば、温度が１００℃～３００℃、圧力が０．２～１０ＭＰａ、時間が０．１～５時間の範囲で実施することができる。また、加熱加圧成形は、真空プレス等を用いて真空状態を０．５～５時間保持する方法を採用できる。 [Laminate]
It is also possible to produce a laminated plate containing the prepreg of the present invention and a metal foil. Specifically, a metal foil is placed on one or both sides of one prepreg of the present invention, or a metal foil is placed on one or both sides of a prepreg obtained by stacking two or more prepregs of the present invention, and then heated. A laminated plate can be obtained by pressure molding. The laminated plate on which the metal foil is arranged may be referred to as a metal-clad laminated plate.
The metal of the metal foil is not particularly limited as long as it is used for electrical insulating materials, but from the viewpoint of conductivity, copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium. , Chromium, or an alloy containing at least one of these metal elements, copper or aluminum, and preferably copper.
The conditions of the heat and pressure molding are not particularly limited, but for example, the temperature may be 100 ° C. to 300 ° C., the pressure may be 0.2 to 10 MPa, and the time may be 0.1 to 5 hours. .. Further, the heat and pressure molding may be carried out by using a vacuum press or the like for holding the vacuum state for 0.5 to 5 hours.
［多層プリント配線板］
　本発明の多層プリント配線板は、本発明のプリプレグ、本発明の樹脂フィルム及び本発明の積層板からなる群から選択される少なくとも１種類を含有してなるものである。本発明の多層プリント配線板は、本発明のプリプレグ、本発明の樹脂フィルム及び本発明の積層板からなる群から選択される少なくとも１種類を用いて、公知の方法によって、穴明け加工、金属めっき加工、金属箔のエッチング等による回路形成加工及び多層化接着加工を行うことによって、多層プリント配線板を製造することができる。 [Multilayer printed wiring board]
The multilayer printed wiring board of the present invention contains at least one selected from the group consisting of the prepreg of the present invention, the resin film of the present invention, and the laminate of the present invention. The multilayer printed wiring board of the present invention is perforated, metal-plated by a known method using at least one selected from the group consisting of the prepreg of the present invention, the resin film of the present invention and the laminate of the present invention. A multilayer printed wiring board can be manufactured by performing processing, circuit formation processing such as etching of metal foil, and multilayer adhesion processing.
　本発明の樹脂組成物、プリプレグ、積層板、樹脂フィルム及び多層プリント配線板は、１０ＧＨｚ以上の高周波信号を扱う電子機器に好適に用いることができる。特に、多層プリント配線板は、ミリ波レーダー用多層プリント配線板として有用である。 The resin composition, prepreg, laminated board, resin film and multilayer printed wiring board of the present invention can be suitably used for electronic devices handling high frequency signals of 10 GHz or higher. In particular, the multilayer printed wiring board is useful as a multilayer printed wiring board for millimeter wave radar.
　以上、本発明の好適な実施形態を説明したが、これらは本発明の説明のための例示であり、本発明の範囲をこれらの実施形態にのみ限定する趣旨ではない。本発明は、その要旨を逸脱しない範囲で、上記実施形態とは異なる種々の態様で実施することができる。 The preferred embodiments of the present invention have been described above, but these are merely examples for explaining the present invention, and the scope of the present invention is not limited to these embodiments. The present invention can be carried out in various modes different from the above-described embodiment without departing from the scope of the invention.
　以下、実施例を挙げて、本発明を具体的に説明する。ただし、本発明は以下の実施例に限定されるものではない。
　なお、各例において、数平均分子量は以下の様にして測定した。
（数平均分子量の測定方法）
　ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により、標準ポリスチレンを用いた検量線から換算した。検量線は、標準ポリスチレン：ＴＳＫｓｔａｎｄａｒｄ ＰＯＬＹＳＴＹＲＥＮＥ（Ｔｙｐｅ；Ａ－２５００、Ａ－５０００、Ｆ－１、Ｆ－２、Ｆ－４、Ｆ－１０、Ｆ－２０、Ｆ－４０）［東ソー株式会社製、商品名］を用いて３次式で近似した。ＧＰＣの測定条件を、以下に示す。
装置：
　ポンプ：Ｌ－６２００型［株式会社日立ハイテクノロジーズ製］
　検出器：Ｌ－３３００型ＲＩ［株式会社日立ハイテクノロジーズ製］
　カラムオーブン：Ｌ－６５５Ａ－５２［株式会社日立ハイテクノロジーズ製］
　カラム：ガードカラム；ＴＳＫ Ｇｕａｒｄｃｏｌｕｍｎ ＨＨＲ－Ｌ＋カラム；ＴＳＫｇｅｌ Ｇ４０００ＨＨＲ＋ＴＳＫｇｅｌ Ｇ２０００ＨＨＲ（すべて東ソー株式会社製、商品名）
　カラムサイズ：６．０×４０ｍｍ（ガードカラム）、７．８×３００ｍｍ（カラム）
溶離液：テトラヒドロフラン
試料濃度：３０ｍｇ／５ｍＬ
注入量：２０μＬ
流量：１．００ｍＬ／分
測定温度：４０℃ Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples.
In each example, the number average molecular weight was measured as follows.
(Measurement method of number average molecular weight)
It was converted from a calibration curve using standard polystyrene by gel permeation chromatography (GPC). The calibration curve is based on standard polystyrene: TSKstandard POLYSTYRENE (Type; A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) [manufactured by Tosoh Corporation, It was approximated by a cubic equation using the product name]. The measurement conditions of GPC are shown below.
apparatus:
Pump: L-6200 type [manufactured by Hitachi High-Technologies Corporation]
Detector: L-3300 RI [Hitachi High-Technologies Corporation]
Column oven: L-655A-52 [Made by Hitachi High-Technologies Corporation]
Column: Guard column; TSK Guardcolumn HHR-L + column; TSKgel G4000HHR + TSKgel G2000HHR (all manufactured by Tosoh Corporation, trade names)
Column size: 6.0 x 40 mm (guard column), 7.8 x 300 mm (column)
Eluent: Tetrahydrofuran Sample concentration: 30 mg / 5 mL
Injection volume: 20 μL
Flow rate: 1.00 mL / min Measurement temperature: 40 ° C
［製造例Ａ－１：ポリフェニレンエーテル誘導体（Ａ－１）の製造］
　温度計、還流冷却管、撹拌装置を備えた加熱及び冷却可能な容積２Ｌのガラス製フラスコ容器に、トルエン、数平均分子量が約１６，０００の原料ポリフェニレンエーテル「ザイロン（登録商標）Ｓ２０２Ａ」（商品名、旭化成株式会社製）１ｍｏｌ、及び２－アリルフェノールを水酸基換算で４ｍｏｌ相当量を投入し、９０～１００℃で撹拌しながら溶解した。
　溶解したことを目視で確認後、ｔ－ブチルペルオキシイソプロピルモノカーボネート及びオクチル酸マンガンを添加し、溶液温度９０～１００℃で６時間、再分配反応させた後、４０℃に冷却して、分子末端にアリル基が置換した有機基を有するポリフェニレンエーテル誘導体（Ａ－１）を得た。この反応溶液を少量取り出し、ＧＰＣ測定（ポリスチレン換算、溶離液：テトラヒドロフラン）を行ったところ、２－アリルフェノールに由来するダブルピークがシングルピークとなり、且つポリフェニレンエーテル化合物の数平均分子量は５，１００であった。
　各成分の使用量を表１に示す。 [Production Example A-1: Production of polyphenylene ether derivative (A-1)]
In a glass flask container with a volume of 2 L capable of heating and cooling, equipped with a thermometer, a reflux condenser, and a stirrer, toluene, a raw material polyphenylene ether having a number average molecular weight of about 16,000 “Zylon (registered trademark) S202A” (commodity) (Asahi Kasei Co., Ltd.) and 2-allylphenol were added in an amount equivalent to 4 mol in terms of hydroxyl groups, and dissolved at 90 to 100 ° C. with stirring.
After visually confirming the dissolution, t-butylperoxyisopropyl monocarbonate and manganese octylate were added, and a redistribution reaction was performed at a solution temperature of 90 to 100 ° C. for 6 hours, followed by cooling to 40 ° C. A polyphenylene ether derivative (A-1) having an allyl-substituted organic group was obtained. When a small amount of this reaction solution was taken out and subjected to GPC measurement (in terms of polystyrene, eluent: tetrahydrofuran), a double peak derived from 2-allylphenol became a single peak, and the number average molecular weight of the polyphenylene ether compound was 5,100. there were.
The amount of each component used is shown in Table 1.
［製造例Ａ－２：ポリフェニレンエーテル誘導体（Ａ－２）の製造］
　製造例Ａ－１において、２－アリルフェノールの仕込み量を表１に記載のとおりに変更したこと以外は同様に操作を行うことによって、分子片末端にアリル基１つが置換した有機基を有するポリフェニレンエーテル誘導体（Ａ－２）を得た。ポリフェニレンエーテル化合物の数平均分子量は３，３００であった。 [Production Example A-2: Production of polyphenylene ether derivative (A-2)]
A polyphenylene having an organic group in which one allyl group is substituted at one terminal of the molecule, except that the amount of 2-allylphenol charged is changed as shown in Table 1 in Production Example A-1. An ether derivative (A-2) was obtained. The number average molecular weight of the polyphenylene ether compound was 3,300.
［製造例Ａ－３：ポリフェニレンエーテル誘導体（Ａ－３）の製造］
　製造例Ａ－１において、２－アリルフェノールの代わりにジアリルビスフェノールＡ（ＤＡＢＰＡ）を使用し、且つ各成分の使用量を表１に記載のとおりにしたこと以外は同様の操作を行うことによって、分子片末端にアリル基２つが置換した有機基を有するポリフェニレンエーテル誘導体（Ａ－３）を得た。ポリフェニレンエーテル化合物の数平均分子量は４，３００であった。 [Production Example A-3: Production of polyphenylene ether derivative (A-3)]
By carrying out the same procedure as in Production Example A-1, except that diallylbisphenol A (DABPA) was used instead of 2-allylphenol, and the amounts of the components used were as shown in Table 1, A polyphenylene ether derivative (A-3) having an organic group in which two allyl groups were substituted at one end of the molecule was obtained. The number average molecular weight of the polyphenylene ether compound was 4,300.
［製造例Ａ－４：ポリフェニレンエーテル誘導体（Ａ－４）の製造］
　製造例Ａ－３において、ＤＡＢＰＡの仕込み量を表１に記載のとおりに変更したこと以外は同様に操作を行うことによって、分子片末端にアリル基２つが置換した有機基を有するポリフェニレンエーテル誘導体（Ａ－４）を得た。ポリフェニレンエーテル化合物の数平均分子量は３，５００であった。 [Production Example A-4: Production of polyphenylene ether derivative (A-4)]
By repeating the same procedure as in Production Example A-3 except that the charged amount of DABPA was changed as shown in Table 1, a polyphenylene ether derivative having an organic group substituted with two allyl groups at one end of the molecule ( A-4) was obtained. The number average molecular weight of the polyphenylene ether compound was 3,500.
［製造例Ａ－５：ポリフェニレンエーテル誘導体（Ａ－５）の製造］
　製造例Ａ－１において、２－アリルフェノールの代わりに下記一般式（１）で表されるアリル基含有化合物（以下、テトラアリルビスフェノール類と称することがある。）を使用し、且つ各成分の使用量を表１に記載のとおりにしたこと以外は同様の操作を行うことによって、分子片末端にアリル基４つが置換した有機基を有するポリフェニレンエーテル誘導体（Ａ－５）を得た。ポリフェニレンエーテル化合物の数平均分子量は５，４００であった。
Figure JPOXMLDOC01-appb-C000036
（式中、Ｘａ２は有機基であり、前記一般式（ａ－５）中のＸａ２と同様に説明される。） [Production Example A-5: Production of polyphenylene ether derivative (A-5)]
In Production Example A-1, an allyl group-containing compound represented by the following general formula (1) (hereinafter sometimes referred to as tetraallyl bisphenols) is used in place of 2-allylphenol, and each of the components is A polyphenylene ether derivative (A-5) having an organic group substituted with four allyl groups at the end of a molecule was obtained by performing the same operation except that the amount used was as shown in Table 1. The number average molecular weight of the polyphenylene ether compound was 5,400.
Figure JPOXMLDOC01-appb-C000036
(In the formula, X a2 is an organic group and is described in the same manner as X a2 in the general formula (a-5).)
［製造例Ａ－６：ポリフェニレンエーテル誘導体（Ａ－６）の製造］
　製造例Ａ－５において、下記一般式（１）で表されるアリル基含有化合物の仕込み量を表１に記載のとおりに変更したこと以外は同様に操作を行うことによって、分子片末端にアリル基４つが置換した有機基を有するポリフェニレンエーテル誘導体（Ａ－６）を得た。ポリフェニレンエーテル化合物の数平均分子量は４，５００であった。 [Production Example A-6: Production of polyphenylene ether derivative (A-6)]
By carrying out the same procedure as in Production Example A-5 except that the charged amount of the allyl group-containing compound represented by the following general formula (1) was changed as shown in Table 1, allyl was added to the terminal of one molecule. A polyphenylene ether derivative (A-6) having an organic group in which four groups were substituted was obtained. The number average molecular weight of the polyphenylene ether compound was 4,500.
［製造例Ａ－７：ポリフェニレンエーテル誘導体（Ａ－７）の製造］
　製造例Ａ－５において、「ザイロン（登録商標）Ｓ２０２Ａ」（商品名、旭化成株式会社製）を「ザイロン（登録商標）Ｓ２０３Ａ」（商品名、旭化成株式会社製）に変更したこと以外は同様に操作を行うことによって、分子片末端にアリル基４つが置換した有機基を有するポリフェニレンエーテル誘導体（Ａ－７）を得た。ポリフェニレンエーテル化合物の数平均分子量は４，２００であった。 [Production Example A-7: Production of polyphenylene ether derivative (A-7)]
The same as in Production Example A-5 except that "Zylon (registered trademark) S202A" (trade name, manufactured by Asahi Kasei Corporation) was changed to "Zylon (registered trademark) S203A" (trade name, manufactured by Asahi Kasei Corporation). By performing the operation, a polyphenylene ether derivative (A-7) having an organic group in which four allyl groups were substituted at the terminal of a molecule was obtained. The number average molecular weight of the polyphenylene ether compound was 4,200.
［製造例Ａ－８：ポリフェニレンエーテル誘導体（Ａ－８）の製造］
　製造例Ａ－７において、下記一般式（１）で表されるアリル基含有化合物の仕込み量を表１に記載のとおりに変更したこと以外は同様に操作を行うことによって、分子片末端にアリル基４つが置換した有機基を有するポリフェニレンエーテル誘導体（Ａ－８）を得た。ポリフェニレンエーテル化合物の数平均分子量は３，８００であった。 [Production Example A-8: Production of polyphenylene ether derivative (A-8)]
The same procedure as in Production Example A-7 was repeated except that the amount of the allyl group-containing compound represented by the following general formula (1) was changed as shown in Table 1. A polyphenylene ether derivative (A-8) having an organic group in which four groups were substituted was obtained. The number average molecular weight of the polyphenylene ether compound was 3,800.
［比較製造例Ａ’－９：ポリフェニレンエーテル誘導体（Ａ’－９）の製造］
　温度計、還流冷却管、撹拌装置を備えた加熱及び冷却可能な容積２Ｌのガラス製フラスコ容器に、トルエン、数平均分子量が約１６，０００の原料ポリフェニレンエーテル「ザイロン（登録商標）Ｓ２０２Ａ」（商品名、旭化成株式会社製）、及びｐ－アミノフェノールを投入し、９０～１００℃で撹拌しながら溶解した。
　溶解したことを目視で確認後、ｔ－ブチルペルオキシイソプロピルモノカーボネート及びナフテン酸マンガンを添加し、溶液温度９０～１００℃で６時間、再分配反応させた後、４０℃に冷却して分子末端に第一級アミノ基を有するポリフェニレンエーテル誘導体を得た。ここで、この反応溶液を少量取り出し、ＧＰＣ測定（ポリスチレン換算、溶離液：テトラヒドロフラン）を行ったところ、ｐ－アミノフェノールに由来するピークが消失し、且つポリフェニレンエーテル化合物の数平均分子量は約１２，０００であった。また少量取り出した反応溶液をメタノール／ベンゼン混合溶媒（混合質量比＝１：１）に滴下し、再沈殿させて精製した固形分のＦＴ－ＩＲ測定を行ったところ、３，４００ｃｍ－１付近の第一級アミノ基由来のピークの出現が確認された。 [Comparative Production Example A′-9: Production of polyphenylene ether derivative (A′-9)]
In a glass flask container with a volume of 2 L capable of heating and cooling, equipped with a thermometer, a reflux condenser, and a stirrer, toluene, a raw material polyphenylene ether having a number average molecular weight of about 16,000 “Zylon (registered trademark) S202A” (commodity) Name, manufactured by Asahi Kasei Co., Ltd.) and p-aminophenol were added and dissolved at 90 to 100 ° C. with stirring.
After visually confirming the dissolution, t-butylperoxyisopropyl monocarbonate and manganese naphthenate were added, and a redistribution reaction was performed at a solution temperature of 90 to 100 ° C. for 6 hours, followed by cooling to 40 ° C. A polyphenylene ether derivative having a primary amino group was obtained. Here, when a small amount of this reaction solution was taken out and subjected to GPC measurement (in terms of polystyrene, eluent: tetrahydrofuran), the peak derived from p-aminophenol disappeared, and the number average molecular weight of the polyphenylene ether compound was about 12, It was 000. The reaction solution taken out a small amount of methanol / benzene mixed solvent (weight ratio = 1: 1) was added dropwise, was subjected to FT-IR measurement of solids were purified by reprecipitation, 3,400 cm -1 vicinity of The appearance of peaks derived from primary amino groups was confirmed.
　次に、上記反応溶液に、ＢＭＩ－４０００（商品名、大和化成工業株式会社製）及びプロピレングリコールモノメチルエーテルを加えて、撹拌しながら液温を昇温し、１００℃で保温しながら４時間反応させた後、冷却及び２００メッシュフィルターを通して濾過することにより、ポリフェニレンエーテル誘導体（Ａ’－９）を製造した。
　この反応溶液を少量取り出し、上記同様に再沈殿、精製した固形物のＦＴ－ＩＲ測定を行い、３，５００ｃｍ－１付近の第一級アミノ基由来ピークの消失と、１，７００～１，７３０ｃｍ－１のカルボニル基の出現が確認された。またこの固形物の数平均分子量は約６，５００であった。
　各成分の使用量を表１に示す。 Next, BMI-4000 (trade name, manufactured by Daiwa Kasei Kogyo Co., Ltd.) and propylene glycol monomethyl ether were added to the above reaction solution, the liquid temperature was raised with stirring, and the reaction was carried out for 4 hours while keeping the temperature at 100 ° C. After that, the polyphenylene ether derivative (A′-9) was manufactured by cooling and filtering through a 200 mesh filter.
A small amount of this reaction solution was taken out, and FT-IR measurement was performed on the solid obtained by reprecipitation and purification in the same manner as above. The disappearance of the primary amino group-derived peak near 3,500 cm −1 and 1,700 to 1,730 cm The appearance of a carbonyl group of -1 was confirmed. The number average molecular weight of this solid substance was about 6,500.
The amount of each component used is shown in Table 1.
Figure JPOXMLDOC01-appb-T000037
Figure JPOXMLDOC01-appb-T000037
　表１における各材料は、以下のとおりである。
（１）ポリフェニレンエーテル
・ザイロン（登録商標）Ｓ２０２Ａ：ポリフェニレンエーテル（旭化成ケミカルズ株式会社製）、数平均分子量＝１６，０００、商品名
・ザイロン（登録商標）Ｓ２０３Ａ：ポリフェニレンエーテル（旭化成ケミカルズ株式会社製）、数平均分子量＝１２，０００、商品名
（２）再分配反応用化合物
・２－アリルフェノール：東京化成工業株式会社製
・ジアリルビスフェノールＡ：２，２－ビス（３－アリル－４－ヒドロキシフェニル）プロパン、大和化成工業株式会社製
・テトラアリルビスフェノール類：下記一般式（１）で表される化合物、群栄化学工業株式会社製
Figure JPOXMLDOC01-appb-C000038
（式（１）中、Ｘａ２は有機基であり、前記一般式（ａ－５）中のＸａ２と同様に説明される。）
・ｐ－アミノフェノール：イハラケミカル工業株式会社製
（３）変性用化合物
・ＢＭＩ－４０００：２，２－ビス［４－（４－マレイミドフェノキシ）フェニル］プロパン、商品名（大和化成工業株式会社製）
（４）反応触媒
・パーブチル（登録商標）Ｉ：ｔ－ブチルペルオキシイソプロピルモノカーボネート（日油株式会社製）
・ナフテン酸マンガン（和光純薬工業株式会社製） Each material in Table 1 is as follows.
(1) Polyphenylene ether Zylon (registered trademark) S202A: Polyphenylene ether (manufactured by Asahi Kasei Chemicals Co., Ltd.), number average molecular weight = 16,000, trade name Zylon (registered trademark) S203A: Polyphenylene ether (manufactured by Asahi Kasei Chemicals Co., Ltd.) , Number average molecular weight = 12,000, trade name (2) compound for redistribution reaction ・ 2-allylphenol: manufactured by Tokyo Chemical Industry Co., Ltd. ・ diallyl bisphenol A: 2,2-bis (3-allyl-4-hydroxyphenyl) ) Propane, manufactured by Daiwa Kasei Kogyo Co., Ltd., tetraallyl bisphenols: compounds represented by the following general formula (1), manufactured by Gunei Chemical Industry Co., Ltd.
Figure JPOXMLDOC01-appb-C000038
(In the formula (1), X a2 is an organic group, and it is described in the same manner as the X a2 in the general formula (a-5).)
-P-aminophenol: manufactured by Ihara Chemical Industry Co., Ltd. (3) modifying compound-BMI-4000: 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, trade name (manufactured by Daiwa Kasei Kogyo Co., Ltd. )
(4) Reaction catalyst Perbutyl (registered trademark) I: t-butyl peroxyisopropyl monocarbonate (manufactured by NOF CORPORATION)
・ Manganese naphthenate (manufactured by Wako Pure Chemical Industries, Ltd.)
［製造例Ｂ－１：ポリアミノビスマレイミド化合物（Ｂ１－１）の製造］
　温度計、還流冷却管、撹拌装置を備えた加熱及び冷却可能な容積１Ｌのガラス製フラスコ容器に、２，２－ビス［４－（４－マレイミドフェノキシ）フェニル］プロパン（マレイミド化合物（ｂ１））、３，３’－ジメチル－５，５’－ジエチル－４，４’－ジフェニルメタンビスマレイミド（マレイミド化合物（ｂ１））、４，４’－［１，３－フェニレンビス（１－メチルエチリデン）］ビスアニリン（ジアミン化合物（ｂ２））及びプロピレングリコールモノメチルエーテルを投入し、液温を１２０℃に保ち、撹拌しながら３時間反応させた後、冷却及び２００メッシュフィルターを通して濾過することにより、数平均分子量８００のポリアミノビスマレイミド化合物（Ｂ１－１）を製造した。
　各成分の使用量を表２に示す。 [Production Example B-1: Production of polyamino bismaleimide compound (B1-1)]
2,2-bis [4- (4-maleimidophenoxy) phenyl] propane (maleimide compound (b1)) was placed in a heatable and coolable 1 L glass flask equipped with a thermometer, a reflux condenser, and a stirrer. , 3,3'-Dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide (maleimide compound (b1)), 4,4 '-[1,3-phenylenebis (1-methylethylidene)] Bisaniline (diamine compound (b2)) and propylene glycol monomethyl ether were added, the liquid temperature was maintained at 120 ° C., the mixture was reacted for 3 hours while stirring, then cooled and filtered through a 200 mesh filter to give a number average molecular weight of 800. The polyamino bismaleimide compound (B1-1) of was produced.
Table 2 shows the amount of each component used.
Figure JPOXMLDOC01-appb-T000039
Figure JPOXMLDOC01-appb-T000039
　表２における各材料は、以下のとおりである。
（１）マレイミド化合物（ｂ１）
・ＢＭＩ－５１００：３，３’－ジメチル－５，５’－ジエチル－４，４’－ジフェニルメタンビスマレイミド、大和化成工業株式会社製、商品名
・ＢＭＩ－４０００：２，２－ビス［４－（４－マレイミドフェノキシ）フェニル］プロパン、大和化成工業株式会社製、商品名
（２）ジアミン化合物（ｂ２）
・ビスアニリン－Ｍ：４，４’－［１，３－フェニレンビス（１－メチルエチリデン）］ビスアニリン、三井化学株式会社製、商品名 Each material in Table 2 is as follows.
(1) Maleimide compound (b1)
BMI-5100: 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, manufactured by Daiwa Kasei Kogyo Co., Ltd., trade name BMI-4000: 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, manufactured by Daiwa Chemical Industry Co., Ltd., trade name (2) diamine compound (b2)
-Bisaniline-M: 4,4 '-[1,3-phenylenebis (1-methylethylidene)] bisaniline, manufactured by Mitsui Chemicals, Inc., trade name
［実施例１～８、比較例１～２］
　表３に記載の各成分を表３に記載の配合量（単位：質量部）に従って室温又は５０～８０℃で加熱しながら撹拌及び混合して、固形分（不揮発分）濃度約５０質量％の樹脂組成物を調製した。
　各例で得た樹脂組成物を、厚さ０．０７ｍｍのガラス布（ＮＥガラス、日東紡績株式会社製）に塗工した後、１０５℃で５分間加熱乾燥して、樹脂含有量（樹脂成分量）約７３質量％のプリプレグを作製した。これらのプリプレグ６枚を重ね、その上下に、厚さ１８μｍのロープロファイル銅箔（ＢＦ－ＡＮＰ１８、Ｍ面のＲｚ：１．５μｍ、古河電気工業株式会社製）をＭ面が接するように配置し、温度２３０℃、圧力４ＭＰａ、時間１８０分間の条件で加熱加圧成形して、両面銅張積層板（厚さ：０．８ｍｍ）を作製した。 [Examples 1 to 8 and Comparative Examples 1 and 2]
Each component shown in Table 3 was stirred and mixed while heating at room temperature or 50 to 80 ° C. according to the blending amount (unit: parts by mass) shown in Table 3 to obtain a solid (nonvolatile) concentration of about 50% by mass. A resin composition was prepared.
The resin composition obtained in each example was applied to a 0.07 mm-thick glass cloth (NE glass, manufactured by Nitto Boseki Co., Ltd.) and then dried by heating at 105 ° C. for 5 minutes to give a resin content (resin component). Amount of about 73 mass% of prepreg was prepared. Six of these prepregs were stacked, and a 18 μm thick low profile copper foil (BF-ANP18, Mz Rz: 1.5 μm, manufactured by Furukawa Electric Co., Ltd.) was placed above and below the prepreg so that the M face was in contact. A double-sided copper-clad laminate (thickness: 0.8 mm) was produced by heat-press molding under conditions of a temperature of 230 ° C., a pressure of 4 MPa, and a time of 180 minutes.
＜評価・測定方法＞
　上記実施例及び比較例で得られた樹脂組成物又は両面銅張積層板を用いて、下記方法に従って各測定及び評価を行った。結果を表３に示す。 <Evaluation / Measurement method>
Using the resin compositions or double-sided copper-clad laminates obtained in the above Examples and Comparative Examples, each measurement and evaluation was performed according to the following methods. The results are shown in Table 3.
（１．樹脂組成物の相容性の評価）
　各例で得た樹脂組成物を目視で観察して、相容性（巨視的（マクロ）な相分離及び析出物の有無）を以下の基準に従い評価した。なお、評価Ａ～Ｃであることが好ましく、Ａ又はＢであることがより好ましく、Ａであることがさらに好ましい。
　Ａ：１週間以上放置しても、巨視的（マクロ）な相分離及び析出物がなかった。
　Ｂ：１日放置しても変化はなかったが、１週間以上放置したところ、析出物はないが、巨視的（マクロ）な相分離が少々生じていた。
　Ｃ：１日放置したところ、析出物はないが、巨視的（マクロ）な相分離が生じていた。
　Ｄ：１日放置後、析出物が確認された。 (1. Evaluation of compatibility of resin composition)
The resin compositions obtained in each example were visually observed, and the compatibility (the presence or absence of macroscopic (macro) phase separation and precipitates) was evaluated according to the following criteria. The evaluations A to C are preferable, A or B is more preferable, and A is further preferable.
A: There was no macroscopic (macro) phase separation or precipitate even after standing for 1 week or longer.
B: There was no change when left for 1 day, but when left for 1 week or longer, there was no precipitate, but some macroscopic phase separation occurred.
C: When left for one day, there was no precipitate, but macroscopic phase separation occurred.
D: After standing for 1 day, a precipitate was confirmed.
（２．両面銅張積層板の誘電特性の評価）
　表３に記載の各成分を表３に記載の配合量（単位：質量部）に従って室温又は５０～８０℃で加熱しながら撹拌及び混合して、固形分（不揮発分）濃度４０～６０質量％の樹脂組成物を調製した。
　各例で得た樹脂組成物を、厚さ３８μｍのＰＥＴフィルム（Ｇ２－３８、帝人株式会社製）に塗工した後、１７０℃で５分間加熱乾燥して、Ｂステージの樹脂フィルムを作製した。当該樹脂フィルムをＰＥＴフィルムから剥離した後、粉砕し、厚さ１ｍｍ、５０ｍｍ×３５ｍｍのサイズに型抜きしたテフロン（登録商標）シートに樹脂を投入し、その上下に、厚さ１８μｍのロープロファイル銅箔（ＢＦ－ＡＮＰ１８、古河電気工業株式会社製）をＭ面が接するように配置し、温度２３０℃、圧力２．０ＭＰａ、時間１２０分間の条件で加熱加圧成形して、両面銅張積層板（厚さ：１ｍｍ）を作製した。
　こうして得られた両面銅張積層板を銅エッチング液である過硫酸アンモニウム（三菱ガス化学株式会社製）１０質量％溶液に浸漬することにより銅箔を取り除いた評価基板から、２ｍｍ×５０ｍｍの評価基板を作製した。
　該評価基板を用いて、１０ＧＨｚ帯における誘電率（Ｄｋ）及び誘電正接（Ｄｆ）を空洞共振器法により得られる共振周波数と無負荷Ｑ値から算出した。測定器には、アジレント・テクノロジー株式会社製のベクトル型ネットワークアナライザＥ８３６４Ｂ、株式会社関東電子応用開発製のＣＰ５３１（１０ＧＨｚ共振器）及びＣＰＭＡ－Ｖ２（プログラム）をそれぞれ使用して、雰囲気温度２５℃で行った。
　誘電率（Ｄｋ）は２．９０以下が好ましく、２．７５以下がより好ましい。誘電正接（Ｄｆ）は０．００５５以下が好ましく、０．００５０以下がより好ましく、０．００４５以下がさらに好ましい。 (2. Evaluation of dielectric properties of double-sided copper clad laminate)
Each component shown in Table 3 is stirred and mixed while heating at room temperature or 50 to 80 ° C. according to the blending amount (unit: parts by mass) shown in Table 3 to obtain a solid (nonvolatile) concentration of 40 to 60% by mass. A resin composition of was prepared.
The resin composition obtained in each example was applied to a PET film (G2-38, manufactured by Teijin Limited) having a thickness of 38 μm, and then heat-dried at 170 ° C. for 5 minutes to prepare a B-stage resin film. . After peeling the resin film from the PET film, the resin was put into a Teflon (registered trademark) sheet that was crushed and die-cut into a size of 1 mm and a size of 50 mm × 35 mm. A foil (BF-ANP18, manufactured by Furukawa Electric Co., Ltd.) is arranged so that the M surface is in contact with it, and heat-pressed under conditions of a temperature of 230 ° C., a pressure of 2.0 MPa and a time of 120 minutes, and a double-sided copper clad laminate. (Thickness: 1 mm) was produced.
A double-sided copper clad laminate thus obtained was immersed in a copper etching solution containing ammonium persulfate (manufactured by Mitsubishi Gas Chemical Co., Inc.) 10% by mass to remove the copper foil, and then a 2 mm × 50 mm evaluation substrate was obtained. It was made.
Using the evaluation board, the dielectric constant (Dk) and the dielectric loss tangent (Df) in the 10 GHz band were calculated from the resonance frequency and the unloaded Q value obtained by the cavity resonator method. Vector network analyzer E8364B manufactured by Agilent Technologies, CP531 (10 GHz resonator) and CPMA-V2 (program) manufactured by Kanto Electronics Co., Ltd. were used as measuring instruments at an ambient temperature of 25 ° C. went.
The dielectric constant (Dk) is preferably 2.90 or less, more preferably 2.75 or less. The dielectric loss tangent (Df) is preferably 0.0055 or less, more preferably 0.0050 or less, and further preferably 0.0045 or less.
Figure JPOXMLDOC01-appb-T000040
Figure JPOXMLDOC01-appb-T000040
　なお、表３における各材料は、以下のとおりである。
（１）ポリフェニレンエーテル誘導体（Ａ）
・ポリフェニレンエーテル誘導体（Ａ－１）～（Ａ－８）：前記製造例Ａ－１～Ａ－８で製造したポリフェニレンエーテル誘導体（Ａ－１）～（Ａ－８）を使用した。
・ポリフェニレンエーテル誘導体（Ａ’－９）：前記製造例Ａ’－９で製造したポリフェニレンエーテル誘導体（Ａ’－９）を使用した。
・ＳＡ９０００：下記式（２）で表される両末端メタクリル変性ポリフェニレンエーテル誘導体、重量平均分子量１，７００（ＳＡＢＩＣイノベーティブプラスチックス社製、商品名）
Figure JPOXMLDOC01-appb-C000041
（式（２）中、ｘ１及びｘ２は、各々独立に、０～２０である。ｘ１及びｘ２の合計は１～３０であることが好ましい。） In addition, each material in Table 3 is as follows.
(1) Polyphenylene ether derivative (A)
-Polyphenylene ether derivatives (A-1) to (A-8): The polyphenylene ether derivatives (A-1) to (A-8) produced in Production Examples A-1 to A-8 were used.
-Polyphenylene ether derivative (A'-9): The polyphenylene ether derivative (A'-9) produced in Production Example A'-9 was used.
SA9000: methacryl-modified polyphenylene ether derivative modified at both ends represented by the following formula (2), weight average molecular weight 1,700 (SABIC Innovative Plastics, trade name)
Figure JPOXMLDOC01-appb-C000041
(In the formula (2), x1 and x2 are each independently 0 to 20. The total of x1 and x2 is preferably 1 to 30.)
（２）マレイミド化合物（Ｂ）
・ポリアミノビスマレイミド化合物（Ｂ－１）：前記製造例Ｂ－１で製造したポリアミノビスマレイミド化合物（Ｂ１－１）を使用した。
（３）スチレン系熱可塑性エラストマー（Ｃ）
・クレイトン（登録商標）Ｇ１６５２：水添スチレン系熱可塑性エラストマー（ＳＥＢＳ）、メルトフローレート５．０ｇ／１０分、スチレン含有量３０％、水素添加率１００％（クレイトンポリマージャパン株式会社製、商品名）
（４）無機充填材（Ｄ）
・シリカ：球状溶融シリカ、平均粒子径＝０．５μｍ
（５）硬化促進剤（Ｅ）
・パーブチル（登録商標）Ｐ：α，α’－ビス（ｔ－ブチルパーオキシ）ジイソプロピルベンゼン（日油株式会社製、商品名）
・Ｇ－８００９Ｌ：イソシアネートマスクイミダゾール（ヘキサメチレンジイソシアネート樹脂と２－エチル－４－メチルイミダゾールの付加反応物）（第一工業製薬株式会社製、商品名）
（６）難燃剤（Ｆ）
・ＰＱ－６０：パラキシリレンビスジフェニルホスフィンオキサイド、晋一化工股▲分▼有限公司製
・ＯＰ９３５：ジアルキルホスフィン酸アルミニウム塩、２置換ホスフィン酸の金属塩、リン含有量；２３．５質量％（クラリアント社製、商品名）
（７）架橋剤（Ｇ）
・Ｂ－１０００：１，２－ポリブタジエンホモポリマー、数平均分子量１，２００（日本曹達株式会社製、商品名） (2) Maleimide compound (B)
-Polyamino bismaleimide compound (B-1): The polyamino bismaleimide compound (B1-1) produced in Production Example B-1 was used.
(3) Styrenic thermoplastic elastomer (C)
Kraton (registered trademark) G1652: hydrogenated styrene thermoplastic elastomer (SEBS), melt flow rate 5.0 g / 10 minutes, styrene content 30%, hydrogenation rate 100% (Kreton Polymer Japan Co., Ltd., trade name )
(4) Inorganic filler (D)
-Silica: spherical fused silica, average particle size = 0.5 μm
(5) Curing accelerator (E)
-Perbutyl (registered trademark) P: α, α'-bis (t-butylperoxy) diisopropylbenzene (trade name, manufactured by NOF CORPORATION)
G-8009L: Isocyanate mask imidazole (addition reaction product of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole) (Daiichi Kogyo Seiyaku Co., Ltd., trade name)
(6) Flame retardant (F)
・ PQ-60: paraxylylene bisdiphenylphosphine oxide, manufactured by Shinichi Chemical Co., Ltd. (Product name)
(7) Crosslinking agent (G)
B-1000: 1,2-polybutadiene homopolymer, number average molecular weight 1,200 (Nippon Soda Co., Ltd., trade name)
　表３に示された結果から明らかなように、本発明の実施例においては、樹脂組成物の相容性が良好又は優れており、これらを用いて作製した銅張積層板は、１０ＧＨｚ帯以上の高周波数帯における誘電特性に優れている。
　一方、比較例１においては、樹脂組成物の相容性が不良であり、１０ＧＨｚ帯以上の高周波数帯における誘電特性も不十分である。また比較例２では、樹脂組成物の相容性は良好となったものの、銅張積層板は、１０ＧＨｚ帯以上の高周波数帯における誘電特性に乏しかった。 As is clear from the results shown in Table 3, in the examples of the present invention, the compatibility of the resin composition is good or excellent, and the copper-clad laminate produced using these has a compatibility of 10 GHz band or higher. Has excellent dielectric characteristics in the high frequency band.
On the other hand, in Comparative Example 1, the compatibility of the resin composition is poor and the dielectric properties in the high frequency band of 10 GHz band or higher are also insufficient. Further, in Comparative Example 2, although the compatibility of the resin composition was good, the copper-clad laminate had poor dielectric properties in the high frequency band of 10 GHz band or higher.
　本発明の樹脂組成物は相容性が良好であり、該樹脂組成物から作製される積層板は特に１０ＧＨｚ帯以上の高周波数帯における誘電特性に優れるため、６ＧＨｚを超える周波数帯の電波が使用される第五世代移動通信システム（５Ｇ）アンテナ及び３０～３００ＧＨｚの周波数帯の電波が使用されるミリ波レーダーに利用される多層プリント配線板に有用である。 The resin composition of the present invention has good compatibility, and since the laminated plate produced from the resin composition has excellent dielectric properties especially in a high frequency band of 10 GHz band or higher, radio waves in a frequency band exceeding 6 GHz are used. It is useful for a fifth-generation mobile communication system (5G) antenna and a multilayer printed wiring board used for a millimeter-wave radar that uses radio waves in the frequency band of 30 to 300 GHz.

Claims (20)

  1. 　（Ａ）不飽和脂肪族炭化水素基が置換した有機基を有するポリフェニレンエーテル誘導体、及び
    　（Ｂ）Ｎ－置換マレイミド基を少なくとも２個有するマレイミド化合物及びその誘導体からなる群から選択される少なくとも１種類、
    を含有してなる、樹脂組成物。     At least one selected from the group consisting of (A) a polyphenylene ether derivative having an organic group substituted with an unsaturated aliphatic hydrocarbon group, and (B) a maleimide compound having at least two N-substituted maleimide groups and a derivative thereof. ,
    A resin composition comprising:
  2. 　前記（Ａ）成分が有する不飽和脂肪族炭化水素基が置換した有機基が下記一般式（ａ－１）で表される構造を有する、請求項１に記載の樹脂組成物。
    Figure JPOXMLDOC01-appb-C000001
    （式（ａ－１）中、Ｒａ１は炭素数２～１０の不飽和脂肪族炭化水素基である。ｍ１は１又は２であり、ｎ１は０又は１である。＊は、他の構造への結合位置を示す。）     The resin composition according to claim 1, wherein the organic group substituted by the unsaturated aliphatic hydrocarbon group contained in the component (A) has a structure represented by the following general formula (a-1).
    Figure JPOXMLDOC01-appb-C000001
    (In the formula (a-1), R a1 is an unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms. M1 is 1 or 2, n1 is 0 or 1. * represents another structure. The binding position to is shown.)
  3. 　前記（Ａ）成分が有する不飽和脂肪族炭化水素基が置換した有機基が下記一般式（ａ－２）で表される構造を有する、請求項１又は２に記載の樹脂組成物。
    Figure JPOXMLDOC01-appb-C000002
    （式（ａ－２）中、Ｒａ２及びＲａ３は、各々独立に、炭素数２～１０の不飽和脂肪族炭化水素基である。＊は、他の構造への結合位置を示す。）     The resin composition according to claim 1 or 2, wherein the organic group substituted by the unsaturated aliphatic hydrocarbon group contained in the component (A) has a structure represented by the following general formula (a-2).
    Figure JPOXMLDOC01-appb-C000002
    (In the formula (a-2), R a2 and R a3 are each independently an unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms. * Represents a bonding position to another structure.)
  4. 　前記（Ａ）成分が有する不飽和脂肪族炭化水素基の合計数が２つ以上である、請求項１～３のいずれか１項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 3, wherein the total number of unsaturated aliphatic hydrocarbon groups contained in the component (A) is 2 or more.
  5. 　前記（Ａ）成分が有する不飽和脂肪族炭化水素基の合計数が４つ以上である、請求項１～４のいずれか１項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 4, wherein the total number of unsaturated aliphatic hydrocarbon groups contained in the component (A) is 4 or more.
  6. 　前記（Ａ）成分において、前記不飽和脂肪族炭化水素基が、ビニル基、イソプロペニル基、アリル基、１－メチルアリル基又は３－ブテニル基である、請求項１～５のいずれか１項に記載の樹脂組成物。 6. The component (A) according to claim 1, wherein the unsaturated aliphatic hydrocarbon group is a vinyl group, an isopropenyl group, an allyl group, a 1-methylallyl group or a 3-butenyl group. The resin composition described.
  7. 　前記（Ｂ）成分が、Ｎ－置換マレイミド基を少なくとも２個有するマレイミド化合物（ｂ１）由来の構造単位とジアミン化合物（ｂ２）由来の構造単位とを有する、請求項１～６のいずれか１項に記載の樹脂組成物。 7. The component (B) has a structural unit derived from a maleimide compound (b1) having at least two N-substituted maleimide groups and a structural unit derived from a diamine compound (b2), according to any one of claims 1 to 6. The resin composition according to.
  8. 　前記（Ｂ）成分が、下記一般式（Ｂ－１）で表されるポリアミノビスマレイミド化合物を含む、請求項１～７のいずれか１項に記載の樹脂組成物。
    Figure JPOXMLDOC01-appb-C000003
    （式（Ｂ－１）中、ＸＢ１及びＸＢ２は、各々独立に、有機基である。）     8. The resin composition according to claim 1, wherein the component (B) contains a polyaminobismaleimide compound represented by the following general formula (B-1).
    Figure JPOXMLDOC01-appb-C000003
    (In formula (B-1), X B1 and X B2 are each independently an organic group.)
  9. 　１０ＧＨｚにおける誘電率が２．９０以下であり、且つ１０ＧＨｚにおける誘電正接が０．００５５以下である、請求項１～８のいずれか１項に記載の樹脂組成物の硬化物。 A cured product of the resin composition according to any one of claims 1 to 8, which has a dielectric constant at 10 GHz of 2.90 or less and a dielectric loss tangent at 10 GHz of 0.0055 or less.
  10. 　請求項１～８のいずれか１項に記載の樹脂組成物を含有してなるプリプレグ。 A prepreg containing the resin composition according to any one of claims 1 to 8.
  11. 　請求項１０に記載のプリプレグと金属箔とを含有してなる積層板。 A laminated plate containing the prepreg according to claim 10 and a metal foil.
  12. 　請求項１～８のいずれか１項に記載の樹脂組成物を含有してなる樹脂フィルム。 A resin film containing the resin composition according to any one of claims 1 to 8.
  13. 　請求項１０に記載のプリプレグ、請求項１１に記載の積層板及び請求項１２に記載の樹脂フィルムからなる群から選択される少なくとも１種類を含有してなる多層プリント配線板。 A multi-layer printed wiring board comprising at least one selected from the group consisting of the prepreg according to claim 10, the laminate according to claim 11 and the resin film according to claim 12.
  14. 　請求項１０に記載のプリプレグ、請求項１１に記載の積層板及び請求項１２に記載の樹脂フィルムからなる群から選択される少なくとも１種類を含有してなるミリ波レーダー用多層プリント配線板。 A multi-layer printed wiring board for millimeter-wave radar, which contains at least one selected from the group consisting of the prepreg according to claim 10, the laminate according to claim 11 and the resin film according to claim 12.
  15. 　不飽和脂肪族炭化水素基が置換した有機基を有するポリフェニレンエーテル誘導体。 A polyphenylene ether derivative having an organic group substituted with an unsaturated aliphatic hydrocarbon group.
  16. 　前記不飽和脂肪族炭化水素基が置換した有機基が下記一般式（ａ－１）で表される構造を有する、請求項１５に記載のポリフェニレンエーテル誘導体。
    Figure JPOXMLDOC01-appb-C000004
    （式（ａ－１）中、Ｒａ１は炭素数２～１０の不飽和脂肪族炭化水素基である。ｍ１は１又は２であり、ｎ１は０又は１である。＊は、他の構造への結合位置を示す。）     The polyphenylene ether derivative according to claim 15, wherein the organic group substituted with the unsaturated aliphatic hydrocarbon group has a structure represented by the following general formula (a-1).
    Figure JPOXMLDOC01-appb-C000004
    (In the formula (a-1), R a1 is an unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms. M1 is 1 or 2, n1 is 0 or 1. * represents another structure. The binding position to is shown.)
  17. 　前記不飽和脂肪族炭化水素基が置換した有機基が下記一般式（ａ－２）で表される構造を有する、請求項１５又は１６に記載のポリフェニレンエーテル誘導体。
    Figure JPOXMLDOC01-appb-C000005
    （式（ａ－２）中、Ｒａ２及びＲａ３は、各々独立に、炭素数２～１０の不飽和脂肪族炭化水素基である。＊は、他の構造への結合位置を示す。）     The polyphenylene ether derivative according to claim 15 or 16, wherein the organic group substituted with the unsaturated aliphatic hydrocarbon group has a structure represented by the following general formula (a-2).
    Figure JPOXMLDOC01-appb-C000005
    (In the formula (a-2), R a2 and R a3 are each independently an unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms. * Represents a bonding position to another structure.)
  18. 　前記不飽和脂肪族炭化水素基の合計数が２つ以上である、請求項１５～１７のいずれか１項に記載のポリフェニレンエーテル誘導体。 The polyphenylene ether derivative according to any one of claims 15 to 17, wherein the total number of the unsaturated aliphatic hydrocarbon groups is 2 or more.
  19. 　前記不飽和脂肪族炭化水素基の合計数が４つ以上である、請求項１５～１８のいずれか１項に記載のポリフェニレンエーテル誘導体。 The polyphenylene ether derivative according to any one of claims 15 to 18, wherein the total number of the unsaturated aliphatic hydrocarbon groups is 4 or more.
  20. 　前記不飽和脂肪族炭化水素基が、ビニル基、イソプロペニル基、アリル基、１－メチルアリル基又は３－ブテニル基である、請求項１５～１９のいずれか１項に記載のポリフェニレンエーテル誘導体。
          The polyphenylene ether derivative according to any one of claims 15 to 19, wherein the unsaturated aliphatic hydrocarbon group is a vinyl group, an isopropenyl group, an allyl group, a 1-methylallyl group or a 3-butenyl group.
PCT/JP2018/041554 2018-11-08 2018-11-08 Resin composition, cured object obtained from resin composition, prepreg, laminate, resin film, multilayered printed wiring board, multilayered printed wiring board for millimeter-wave radar, and poly(phenylene ether) derivative WO2020095422A1 (en)

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WO2022145377A1 (en) * 2020-12-28 2022-07-07 昭和電工マテリアルズ株式会社 Resin composition, prepreg, laminated plate, resin film, print wiring board, and semiconductor package
KR20230160853A (en) 2021-03-24 2023-11-24 파나소닉 아이피 매니지먼트 가부시키가이샤 Resin composition, prepreg, resin-added film, resin-added metal foil, metal-clad laminate, and wiring board
WO2023090351A1 (en) * 2021-11-18 2023-05-25 株式会社レゾナック Resin composition, prepreg, laminated board, resin film, printed wiring board, and semiconductor package

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