JP2017071689A - Resin composition, prepreg, laminate, multilayer printed board and method for manufacturing multilayer printed board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition having excellent high frequency properties (low dielectric constant and low dielectric loss tangent) and heat resistance, and a prepreg, a laminate and a multilayer printed board prepared therewith.SOLUTION: A resin composition comprises a polyphenylene ether derivative (A) having at least one N-substituted maleimide structure-containing group in a molecule.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition containing a polyphenylene ether derivative, a prepreg, a laminate, a multilayer printed wiring board, and a method for producing a multilayer printed wiring board.

  In mobile communication devices typified by mobile phones, network infrastructure devices such as base station devices, servers and routers, or large computers, etc., the speed and capacity of signals used are increasing year by year. As a result, printed circuit boards mounted on these electronic devices are required to support higher frequencies, and dielectric properties (low dielectric constant and low dielectric loss tangent; below) that enable transmission loss to be reduced. There is a demand for a substrate material that is excellent in high-frequency characteristics. In recent years, as an application for handling such high-frequency signals, in addition to the electronic devices described above, a new system that handles high-frequency wireless signals in the ITS (Intelligent Transport Systems) field (related to automobiles and transportation systems) and indoor short-range communication fields as well. Practical application and practical plans are progressing, and it is expected that a substrate material with low transmission loss will be further required for printed wiring boards mounted on these devices.

  In addition, due to recent environmental problems, mounting of electronic components with lead-free solder and flame-retardant with halogen-free has been required, so printed circuit board materials have higher heat resistance and flame resistance than before. Sex is needed.

  Conventionally, polyphenylene ether (PPE) resin has been used as a heat-resistant thermoplastic polymer having excellent high-frequency characteristics for printed wiring boards that require low transmission loss. For example, a method in which polyphenylene ether and a thermosetting resin are used in combination has been proposed. Specifically, a resin composition containing polyphenylene ether and an epoxy resin (see, for example, Patent Document 1), a resin composition containing polyphenylene ether and a cyanate resin having a low dielectric constant among thermosetting resins ( For example, see Patent Document 2).

  However, the resin compositions described in Patent Documents 1 and 2 are generally insufficient in high-frequency characteristics in the GHz region, adhesion to conductors, low thermal expansion coefficient, and flame retardancy, The heat resistance may decrease due to the low compatibility with the curable resin.

  On the other hand, the present inventors have also made a semi-IPN (semi-interpenetrating network) compatible in the production stage (A stage stage) of a resin composition containing an organic solvent based on a polyphenylene ether resin and a polybutadiene resin. Proposed a resin composition (see, for example, Patent Document 3) that can improve the properties, heat resistance, low thermal expansion coefficient, adhesion to a conductor, and the like. However, in recent years, PCB materials for printed wiring boards have high adhesion to conductors, a low coefficient of thermal expansion, a high thermal resistance, due to demands for higher density, higher reliability, and environmental friendliness. There are ongoing needs such as glass transition temperature and high flame retardancy.

  In addition, printed circuit board materials used in network-related equipment such as servers and routers must be multi-layered as the density increases, requiring high reflow heat resistance and through-hole reliability. Has been. Furthermore, as the high frequency characteristics, excellent dielectric characteristics in a higher frequency band are required, and generally, the substrate material tends to have a higher dielectric loss tangent as the frequency increases, but the conventional 1-5 GHz There is an increasing need for exhibiting excellent dielectric characteristics (low dielectric constant and low dielectric loss tangent) in the 10 GHz band or higher, instead of the dielectric characteristic values in FIG.

Japanese Patent Laid-Open No. 58-069046 Japanese Patent Publication No. 61-018937 JP 2008-95061 A

  In view of the current situation, the present invention provides a resin composition having excellent high-frequency characteristics (low dielectric constant and low dielectric loss tangent), low thermal expansion coefficient, flame retardancy, and high glass transition temperature, and a prepreg and a laminate using the same. It is an object to provide a board and a multilayer printed wiring board.

  As a result of intensive studies to solve the above problems, the present inventors have found that a resin composition containing a polyphenylene ether derivative having a specific molecular structure and a specific inorganic filler has excellent high-frequency characteristics and excellent It has been found that it has excellent heat resistance, high adhesion to a conductor, high glass transition temperature, low thermal expansion coefficient, and high flame retardancy, and has completed the present invention.

That is, the present invention relates to the following [1] to [12].
[1] A resin composition containing a polyphenylene ether derivative (A) having at least one N-substituted maleimide structure-containing group in the molecule.
[2] The polyphenylene ether derivative (A) having at least one N-substituted maleimide structure-containing group in the molecule has a structural unit represented by the following general formula (I), Resin composition.

(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.)
[3] The resin composition according to the above [2], wherein the N-substituted maleimide structure-containing group is a group represented by the following general formula (Z).

(In the formula, each R ² independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. Y represents an integer of 0 to 4. A ¹ represents the following general formula (II), ( III), a group represented by (IV) or (V).)

(In the formula, each R ³ independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. P is an integer of 0 to 4.)

(In the formula, R ⁴ and R ⁵ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. A ² is an alkylene group having 1 to 5 carbon atoms and an alkylidene having 2 to 5 carbon atoms. A group, an ether group, a sulfide group, a sulfonyl group, a carbooxy group, a keto group, a single bond or a group represented by the following general formula (III-1): q and r are each independently an integer of 0 to 4. .)

(In the formula, R ⁶ and R ⁷ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. A ³ is an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, an ether group, A sulfide group, a sulfonyl group, a carboxyl group, a keto group, or a single bond, and s and t are each independently an integer of 0 to 4.)

(In the formula, n is an integer of 0 to 10.)

(In the formula, R ⁸ and R ⁹ 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.)
[4] In the above [3], A ¹ in the general formula (Z) is a group represented by any of the following formulas (A-1), (A-2), and (A-3): The resin composition as described.

[5] The resin composition according to any one of [2] to [4], wherein the structural unit represented by the general formula (I) is a structural unit represented by the following formula (I ′). object.

[6] Any of the above-mentioned [1] to [5], further comprising at least one curing accelerator (B) selected from the group consisting of an organic peroxide, an imidazole curing accelerator, and a phosphorus curing accelerator. 2. The resin composition according to item 1.
[7] The resin composition according to any one of [1] to [6], further including at least one thermosetting resin (C) selected from an epoxy resin, a cyanate ester resin, and a maleimide compound.
[8] The thermosetting resin (C) is a maleimide compound (a) having at least two N-substituted maleimide structure-containing groups in the molecule or an aminobismaleimide compound (c) represented by the following general formula (VI) ), The resin composition according to the above [7].

(In the formula, A ⁴ is the same as the definition of A ^{1 in} the general formula (Z), and A ⁵ is a group represented by the following general formula (VII).)

^{(Wherein, R 17} and ^{R 18} each independently, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, .A ⁸ is an alkoxy group, a hydroxyl group or a halogen atom having 1 to 5 carbon atoms, 1 to carbon atoms 5 alkylene group, alkylidene group having 2 to 5 carbon atoms, ether group, sulfide group, sulfonyl group, carbooxy group, keto group, fluorenylene group, single bond, or the following general formula (VII-1) or (VII-2) Q ′ and r ′ are each independently an integer of 0 to 4.)

(In the formula, R ¹⁹ and R ²⁰ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. A ⁹ is an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, m- or a p-phenylenediisopropylidene group, an ether group, a sulfide group, a sulfonyl group, a carbooxy group, a keto group, or a single bond, and s ′ and t ′ are each independently an integer of 0 to 4.)

(Wherein R ²¹ is an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. A ¹⁰ and A ¹¹ are each independently an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, an ether group, A sulfide group, a sulfonyl group, a carbooxy group, a keto group, or a single bond, w is an integer of 0 to 4.)
[9] A prepreg comprising the resin composition according to any one of [1] to [8] above and a sheet-like fiber reinforced base material.
[10] A laminate having a cured product of the resin composition according to any one of [1] to [8] and a metal foil.
[11] A multilayer printed wiring board having the cured product of the resin composition according to any one of [1] to [8] or the laminated board according to [10].
[12] A method for producing a multilayer printed wiring board, comprising a step of heat-pressing the prepreg according to [9] or the laminate according to [10].

  The resin composition of the present invention has excellent high frequency characteristics (low dielectric constant and low dielectric loss tangent), low thermal expansion coefficient, flame retardancy, and high glass transition temperature. Moreover, when the resin composition of this invention contains a hardening accelerator (B), the further outstanding heat resistance can be added. Therefore, the prepreg and laminated board obtained using this resin composition can be used suitably for electronic component uses, such as a multilayer printed wiring board.

  Hereinafter, embodiments of the present invention will be described in detail. In this specification, a numerical range that is greater than or equal to X and less than or equal to Y (X and Y are real numbers) may be expressed as “X to Y”. For example, the description “0.1-2” indicates a numerical range that is 0.1 or more and 2 or less, and the numerical range includes 0.1, 0.34, 1.03, 2, and the like.

[Resin composition]
One embodiment of the present invention is a polyphenylene ether derivative (A) having at least one N-substituted maleimide structure-containing group in the molecule [hereinafter sometimes simply referred to as a polyphenylene ether derivative (A) or a component (A). ] The resin composition containing this. The resin composition preferably contains at least one curing accelerator (B) selected from the group consisting of an organic peroxide, an imidazole curing accelerator, and a phosphorus curing accelerator.

(Polyphenylene ether derivative (A))
The polyphenylene ether derivative (A) can be used without particular limitation as long as it is a polyphenylene ether derivative having at least one N-substituted maleimide structure-containing group in the molecule.

  In particular, since the polyphenylene ether derivative (A) has at least one N-substituted maleimide structure-containing group in the molecule, it has excellent high-frequency characteristics (low dielectric constant, low dielectric loss tangent), high adhesion to a conductor, high The resin composition has a glass transition temperature, a low thermal expansion coefficient, and high flame retardancy. Here, the thermal expansion coefficient referred to in the present invention is a value called a linear expansion coefficient. The N-substituted maleimide structure-containing group is not particularly limited as long as it contains an N-substituted maleimide group.

  From the same viewpoint as described above, the polyphenylene ether derivative (A) preferably has at least one N-substituted maleimide structure-containing group and a structural unit represented by the following general formula (I) in the molecule. .

(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.)
Examples of the aliphatic hydrocarbon group represented by R ¹ in the general formula (I) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n -A pentyl group etc. are mentioned. The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and more preferably a methyl group. Moreover, as a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example. The halogen atom is preferably a fluorine atom from the viewpoint of halogen-free.

Among the above, R ¹ is preferably an aliphatic hydrocarbon group having 1 to 5 carbon atoms.

x is an integer of 0 to 4, preferably an integer of 0 to 2, and preferably 2. When x is 1 or 2, R ¹ may be substituted at the ortho position on the benzene ring (provided that the substitution position of the oxygen atom is a reference). When x is 2 or more, the plurality of R1s may be the same or different.

  Specifically, the structural unit represented by the general formula (I) is preferably a structural unit represented by the following general formula (I ′).

  The N-substituted maleimide structure-containing group of the polyphenylene ether derivative (A) includes two maleimide groups from the viewpoints of high-frequency properties, adhesion to conductors, heat resistance, glass transition temperature, thermal expansion coefficient, and flame retardancy. A group containing a bismaleimide structure in which nitrogen atoms are bonded via an organic group is preferable, and a group represented by the following general formula (Z) is preferable.

(In the formula, each R ² independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. Y is an integer of 0 to 4. A ¹ represents the following general formula (II), ( III), a group represented by (IV) or (V).)

The aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R ² are explained in the same manner as in R ¹ .

y is an integer of 0 to 4, preferably an integer of 0 to 2, and preferably 0. When y is an integer of 2 or more, the plurality of R ² may be the same or different.

A ¹ represents, formula (II), the group represented by (III), (IV) or (V) are as follows.

(In the formula, each R ³ independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. P is an integer of 0 to 4.)
The aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R ³ are explained in the same manner as in R 1.

p is an integer of 0 to 4, and is preferably an integer of 0 to 2, preferably 0 or 1, and preferably 0 from the viewpoint of availability. When p is an integer of 2 or more, the plurality of R ³ may be the same or different.

(In the formula, R ⁴ and R ⁵ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. A ² is an alkylene group having 1 to 5 carbon atoms and an alkylidene having 2 to 5 carbon atoms. A group, an ether group, a sulfide group, a sulfonyl group, a carbooxy group, a keto group, a single bond or a group represented by the following general formula (III-1): q and r are each independently an integer of 0 to 4. .)
Aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R ⁴ and R ^5, examples of the halogen atom include the same ones as for R ^1. The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, preferably a methyl group or an ethyl group, and more preferably an ethyl group.

Examples of the alkylene group having 1 to 5 carbon atoms represented by A ² include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, and a 1,5-pentamethylene group. Is mentioned. The alkylene group is preferably an alkylene group having 1 to 3 carbon atoms from the viewpoint of high-frequency characteristics, adhesion to a conductor, heat resistance, glass transition temperature, thermal expansion coefficient, and flame retardancy, and is a methylene group. Preferably there is.

Examples of the alkylidene group having 2 to 5 carbon atoms represented by A 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 is preferable from the viewpoints of high-frequency characteristics, adhesion to a conductor, heat resistance, glass transition temperature, thermal expansion coefficient, and flame retardancy.

A ² is preferably an alkylene group having 1 to 5 carbon atoms or an alkylidene group having 2 to 5 carbon atoms among the above options.

q and r are each independently an integer of 0 to 4, and from the viewpoint of availability, both are preferably integers of 0 to 2, and preferably 0 or 2. When q or r is an integer greater than or equal to 2, several R < ⁴ > or R < ⁵ > may be same or different, respectively.

Incidentally, the group represented by the general formula represented by ^{A 2} (III-1) are as follows.

(In the formula, R ⁶ and R ⁷ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. A ³ is an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, an ether group, A sulfide group, a sulfonyl group, a carbooxy group, a keto group, or a single bond, and s and t are each independently 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 ⁶ and R ⁷ are the same as those for R ⁴ and R ⁵ .

As the alkylene group having 1 to 5 carbon atoms represented by A ^3, include those similar to the alkylene group having 1 to 5 carbon atoms represented by A ^2.

As A ³ , among the above options, an alkylidene group having 2 to 5 carbon atoms may be selected.

s and t are integers of 0 to 4, and from the viewpoint of availability, both are preferably integers of 0 to 2, preferably 0 or 1, and preferably 0. When s or t is an integer of 2 or more, a plurality of R ^{6 s} or R ^{7 s} may be the same or different.

(In the formula, n is an integer of 0 to 10.)
From the viewpoint of availability, n is preferably 0 to 5, and preferably 0 to 3.

(In the formula, R ⁸ and R ⁹ 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 and the halogen atom represented by R ⁸ and R ⁹ are described in the same manner as in R ¹ .

  u is an integer of 1 to 8, preferably an integer of 1 to 3, and preferably 1.

A ¹ in the group represented by the general formula (Z) is represented by the following formula (A-) from the viewpoint of high-frequency characteristics, adhesion to a conductor, heat resistance, glass transition temperature, thermal expansion coefficient, and flame retardancy. It is preferable that it is group represented by either 1), (A-2), and (A-3).

  The polyphenylene ether derivative (A) is preferably a polyphenylene ether derivative represented by the following general formula (A ′).

(In the formula, A ¹ , R ¹ , R ² , x and y are as defined above. M is an integer of 1 or more.)
m is preferably an integer of 1 to 300, preferably an integer of 10 to 300, preferably an integer of 30 to 200, and preferably an integer of 50 to 150.

  The polyphenylene ether derivative (A) is preferably a polyphenylene ether derivative represented by any one of the following formulas (A′-1) to (A′-3).

(In the formula, m is the same as m in the general formula (A ′).)

  From the viewpoint that the raw material is inexpensive, the polyphenylene ether derivative of the above formula (A′-1) is preferable, and from the viewpoint of excellent dielectric properties and low water absorption, the above formula (A′-2) A polyphenylene ether derivative is preferred, and a polyphenylene ether derivative of the above formula (A′-3) is preferred from the viewpoint of excellent adhesion to a conductor and mechanical properties (elongation, breaking strength, etc.). Accordingly, one polyphenylene ether derivative represented by any one of the above formulas (A′-1) to (A′-3) is used alone or in combination of two or more in accordance with the intended characteristics. Can do.

  The number average molecular weight of the polyphenylene ether derivative (A) of the present invention is preferably 5000 to 12000, more preferably 7000 to 12000, and still more preferably 7000 to 10,000. When the number average molecular weight is 5000 or more, a better glass transition temperature tends to be obtained in the resin composition of the present invention, prepregs and laminates using the resin composition. Moreover, when a number average molecular weight is 12000 or less, when the resin composition of this invention is used for a laminated board, it exists in the tendency for a more favorable moldability to be obtained.

  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. The value obtained by the method.

(Production method of polyphenylene ether derivative (A))
The polyphenylene ether derivative (A) can be obtained, for example, by the following production method.

  First, a known redistribution of an aminophenol compound represented by the following general formula (VIII) [hereinafter referred to as aminophenol compound (VIII)] and, for example, polyphenylene ether having a number average molecular weight of 15,000 to 25000 in an organic solvent. By reacting, the polyphenylene ether compound (A ″) having a primary amino group in the molecule while reducing the molecular weight of the polyphenylene ether (hereinafter, also simply referred to as polyphenylene ether compound (A ″)). Next, the polyphenylene ether compound (A ″) and the bismaleimide compound represented by the general formula (IX) [hereinafter referred to as bismaleimide compound (IX)]. ] Can be produced by a Michael addition reaction to produce a polyphenylene ether derivative (A).

(In the formula, R ² and y are the same as those in the general formula (Z).)

(In the formula, A ¹ is the same as that in the general formula (Z).)

  Examples of the aminophenol compound (VIII) include o-aminophenol, m-aminophenol, p-aminophenol, and the like. Among these, m-aminophenol and p-aminophenol are used from the viewpoint of the reaction yield when producing the polyphenylene ether compound (A ″) and the heat resistance when the resin composition, prepreg and laminate are used. It is preferable that it is p-aminophenol.

  The molecular weight of the polyphenylene ether compound (A ″) can be controlled by the amount of aminophenol compound (VIII) used. The greater the amount of aminophenol compound (VIII) used, the lower the polyphenylene ether compound (A ″) obtained. Molecular weight. That is, the use amount of the aminophenol compound (VIII) 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 compounding amount of the aminophenol compound (VIII) is not particularly limited. For example, when the number average molecular weight of the polyphenylene ether to be reacted with the aminophenol compound (VIII) is 15,000 to 25000, the polyphenylene ether By using it in the range of 0.5 to 6 parts by mass with respect to 100 parts by mass, a polyphenylene ether derivative (A) having a number average molecular weight of 5000 to 12000 is obtained.

  The organic solvent used in the production process of the polyphenylene ether compound (A ″) is not particularly limited. For example, alcohols such as methanol, ethanol, butanol, butyl cellosolve, ethylene glycol monomethyl ether, propylene glycol monomethyl ether; acetone, methyl ethyl ketone , Ketones such as methyl isobutyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and mesitylene; esters such as methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate and ethyl acetate; N, N-dimethylformamide, N, N -Nitrogen-containing compounds such as dimethylacetamide and N-methyl-2-pyrrolidone. These may be used alone or in combination of two or more. Among these, toluene, xylene, and mesitylene are preferable from the viewpoint of solubility.

  In the production process of the polyphenylene ether compound (A ″), a reaction catalyst can be used as necessary. As this reaction catalyst, a known reaction catalyst in a redistribution reaction can be applied. For example, from the viewpoint of obtaining a polyphenylene ether compound (A ″) having a stable number average molecular weight with good reproducibility, an organic peroxide such as t-butylperoxyisopropyl monocarbonate and a metal carboxylate such as manganese naphthenate May be used in combination. The amount of reaction catalyst used is not particularly limited. For example, from the viewpoint of reaction rate and gelation suppression when producing the polyphenylene ether compound (A ″), the organic peroxide is 0 with respect to 100 parts by mass of the polyphenylene ether to be reacted with the aminophenol compound (VIII). It is good also considering 0.05-5 mass parts and 0.05-0.5 mass parts of carboxylic acid metal salt.

  A predetermined amount of the aminophenol compound (VIII), the polyphenylene ether having a number average molecular weight of 15,000 to 25,000, an organic solvent, and, if necessary, a reaction catalyst is charged into a reactor, and the reaction is carried out while heating, keeping warm, and stirring. '') Is obtained. For the reaction temperature and reaction time in this step, the reaction conditions for known redistribution reactions can be applied.

  From the viewpoint of workability and suppression of gelation, and from the viewpoint of controlling the molecular weight of the polyphenylene ether compound (A ″) for obtaining the component (A) having a desired number average molecular weight, for example, the reaction temperature is 70 to 110. You may react by (degreeC) and reaction time 1-8 hours.

  The solution of the polyphenylene ether compound (A ″) produced as described above may be continuously supplied to the production process for the polyphenylene ether derivative (A) in the next step as it is. At this time, the solution of the polyphenylene ether compound (A ″) may be cooled, or may be adjusted to the reaction temperature in the next step. Further, as described later, this solution may be concentrated as necessary to remove a part of the organic solvent, or may be diluted by adding an organic solvent.

  Examples of the bismaleimide compound (IX) used in producing the polyphenylene ether derivative (A) 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-phenylenebismaleimide, 2, 2-bis (4- (4-maleimidophenoxy) phenyl) propane, bis (4-maleimidophenyl) sulfone, bis (4-maleimidophenyl) sulfide, bis (4-maleimidophenyl) ketone, 2,2-bis (4 -(4-maleimidophenoxy) phenyl) propane, Scan (4- (4-maleimide phenoxy) phenyl) sulfone, 4,4'-bis (3-maleimido phenoxy) biphenyl, 1,6-bismaleimide - (2,2,4-trimethyl) hexane and the like. These may be used alone or in combination of two or more.

  Among these, from the viewpoint of high reaction rate and higher heat resistance, bis (4-maleimidophenyl) methane, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide, 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane may be selected.

  Bis (4-maleimidophenyl) methane may be used from the viewpoint that a polyphenylene ether derivative including the polyphenylene ether derivative represented by the formula (A′-1) is obtained and is inexpensive.

  From the viewpoint of obtaining a polyphenylene ether derivative containing the polyphenylene ether derivative represented by the formula (A′-2), having excellent dielectric properties and low water absorption, 3,3′-dimethyl-5,5′- Diethyl-4,4′-diphenylmethane bismaleimide may be used.

  From the viewpoint that a polyphenylene ether derivative containing the polyphenylene ether derivative represented by the formula (A′-3) is obtained and excellent in high adhesion to a conductor and mechanical properties (elongation, breaking strength, etc.), 2,2- Bis (4- (4-maleimidophenoxy) phenyl) propane may be used.

The amount of bismaleimide compound (IX) used is determined by the amount of aminophenol compound (VIII) used. That is, even if the equivalent ratio (Tb1 / Ta1) of the —NH ₂ group equivalent (Ta1) of the aminophenol compound (VIII) to the maleimide group equivalent (Tb1) of the bismaleimide compound (IX) is in the range of 2 to 6. You may mix | blend in the range of 2-4. By using the bismaleimide compound (IX) within the above equivalent ratio range, better heat resistance, high glass transition temperature and high flame retardancy can be obtained in the resin composition, prepreg and laminate of the present invention. It tends to be.

  In the Michael addition reaction for producing the polyphenylene ether derivative (A), a reaction catalyst can be used as necessary. Although it does not specifically limit as a reaction catalyst which can be used, For example, acidic catalysts, such as p-toluenesulfonic acid; Amines, such as a triethylamine, a pyridine, and a tributylamine; Imidazole compounds, such as methylimidazole and phenylimidazole; Triphenylphosphine, etc. Examples thereof include phosphorus-based catalysts. These may be used alone or in combination of two or more. The amount of the reaction catalyst is not particularly limited, but is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the polyphenylene ether compound (A ″), for example.

  A predetermined amount of the bismaleimide compound (IX) and, if necessary, a reaction catalyst are charged into a polyphenylene ether compound (A ″) solution and subjected to a Michael addition reaction to obtain a polyphenylene ether derivative (A). This step is preferably performed while heating, keeping warm, and stirring. As reaction conditions, from the viewpoint of workability and gelation suppression, for example, the reaction temperature is 50 to 160 ° C., and the reaction time is in the range of 1 to 10 hours. Preferably there is. In this step, as described above, the organic solvent can be added or concentrated to adjust the reaction concentration (solid content concentration) and the solution viscosity. As the organic solvent used additionally, the organic solvent exemplified in the production process of the polyphenylene ether compound (A ″) can be applied, and these may be used alone or in combination of two or more. Good. Among these, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether, N, N-dimethylformamide, and N, N-dimethylacetamide may be selected from the viewpoint of solubility.

  Moreover, the reaction concentration (solid content concentration) in the production process of the polyphenylene ether derivative (A) and the polyphenylene ether compound (A ″) is not particularly limited, but for example, any of the production processes described above is 10 to 60% by mass. It is preferable that it is 20-50 mass%. When the reaction concentration is 10% by mass or more, the reaction rate does not become too slow and tends to be more advantageous in terms of production cost. Further, when the reaction temperature is 60% by mass or less, better solubility tends to be obtained. In addition, the solution viscosity is low, the stirring efficiency is good, and gelation tends to be less.

  In addition, after manufacturing a polyphenylene ether derivative (A), a viewpoint of workability | operativity at the time of taking out from a reactor and various thermosetting resins etc. are added to a polyphenylene ether derivative (A), and it is set as the resin composition of this invention. From the viewpoint of setting the solution viscosity and solution concentration suitable for the actual use situation (for example, solution viscosity and solution concentration suitable for prepreg production), a part or all of the organic solvent in the solution is appropriately removed and concentrated. Alternatively, it may be diluted by adding an organic solvent. There is no restriction | limiting in particular in the organic solvent at the time of adding, One or more types of organic solvents mentioned above are applicable.

  The formation of the polyphenylene ether compound (A ″) and the polyphenylene ether derivative (A) obtained by the above production process can be confirmed by GPC measurement and IR measurement after taking out a small amount of sample after completion of each process.

First, the polyphenylene ether compound (A ″) has a molecular weight lower than that of the starting polyphenylene ether from the GPC measurement, and the peak of the raw material aminophenol compound (VIII) has disappeared. It can be confirmed that the desired polyphenylene ether compound (A ″) is produced by the appearance of a primary amino group of 3500 cm ⁻¹ . In addition, after purifying by reprecipitation, the polyphenylene ether derivative (A) was confirmed to disappear from the peak of the primary amino group of 3300 to 3500 cm ⁻¹ and the appearance of the peak of the carbonyl group of maleimide at 1700 to 1730 cm ⁻¹ from IR measurement. By doing this, it can be confirmed that the desired polyphenylene ether derivative (A) is produced.

  The resin composition of the present invention is more adhesive to conductors, thermal expansion coefficient, flame retardancy, workability than the resin composition containing the polyphenylene ether compound (A ″) and the component (C) described later. It tends to be more excellent (drilling, cutting).

  The resin composition of the present invention comprises at least one curing accelerator (B) selected from the group consisting of an organic peroxide, an imidazole curing accelerator, and a phosphorus curing accelerator in addition to the component (A) described above. It is preferable to contain. By including the component (B), heat resistance and the like can be further improved.

  The organic peroxide is not particularly limited. For example, methyl ethyl ketone peroxide, methyl acetoacetate peroxide, acetylacetoperoxide, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t- Butylperoxy) butane, t-butyl hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxide) Oxy) hexyne, acetyl peroxide, octanoyl peroxide, lauroyl peroxide, benzoyl peroxide, m-toluyl peroxide, diisopropyl peroxydicarbonate, t-butyl peroxyisopropyl monocarbonate 1,1-di (t-hexylperoxy) cyclohexane, t-butylene peroxybenzoate, n-butyl-4,4-di- (t-butylperoxy) -valerate, p-menthane hydroperoxide, diisopropylbenzene, Hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumin hydroperoxide, di (2-t-butylperoxyisopropyl) benzene, dicumyl peroxide, diisopropylbenzene hydroperoxide, 2, 5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-hexyl peroxide, di-t-butyl peroxide, bis (1-phenyl-1- Methylethyl) peroxide, α, α′-bis ( - butylperoxy) diisopropylbenzene, and the like.

  From the viewpoint of further improving heat resistance, organic peroxides include t-butyl peroxyisopropyl monocarbonate, 1,1-di (t-hexylperoxy) cyclohexane, bis (1-phenyl-1-methylethyl) peroxide. , Diisopropylbenzene hydroperoxide, or α, α′-bis (t-butylperoxy) diisopropylbenzene is preferably contained.

From the viewpoint of storage stability and coatability, the organic oxide preferably has a 1 minute half-life temperature of 140 ° C. or higher, more preferably 160 ° C. or higher. The half-life temperature for 1 minute is a solvent inert to radicals such as benzene, and a 0.1 mol / L organic peroxide solution is prepared and thermally decomposed in a glass container substituted with nitrogen to obtain the amount of active oxygen. Is obtained by measuring the temperature at which the halving is halved in 1 minute.

Examples of the imidazole curing accelerator include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2 -Heptadecylimidazole, 4,5-diphenylimidazole, 2-methylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2-heptadecylimidazoline, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-phenyl- Examples include 4-methylimidazole, 2-ethylimidazoline, 2-isopropylimidazoline, 2,4-dimethylimidazoline, 2-phenyl-4-methylimidazoline.

  From the viewpoint of storage stability of the varnish, the imidazole curing accelerator is preferably masked imidazole masked with a masking agent. Examples of the masking agent include acrylonitrile, phenylene diisocyanate, toluidine isocyanate, naphthalene diisocyanate, methylene bisphenyl isocyanate, melamine acrylate, hexamethylene diisocyanate and the like.

  Examples of phosphorus curing accelerators include secondary amines such as morpholine, piperidine, pyrrolidine, dimethylamine, diethylamine, dicyclohexylamine, N-alkylarylamine, piperazine, diallylamine, thiazoline, thiomorpholine; benzyldimethylamine, 2- Tertiary amines such as (dimethylaminomethyl) phenol, 2,4,6-tris (diaminomethyl) phenol; tetrabutylammonium iodide, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium fluoride, chloride Quaternary ammonium such as benzalkonium, benzyldi (2-hydroxyethyl) ethylammonium chloride, decyldi (2-hydroxyethyl) methylammonium bromide And the like.

  Component (B) may be used alone or in combination of two or more. From the viewpoint of heat resistance, glass transition temperature and thermal expansion coefficient, imidazole curing agent and organic peroxide are used as component (B). It is more preferable to contain. From the viewpoint described above, it is more preferable to contain an organic oxide having a 1 minute half-life temperature of 140 ° C. or higher and a mask imidazole.

  The content ratio of component (B) is not particularly limited. For example, 100 parts by mass of component (A) of the present invention (however, when component (C) described later is used, component (A) and component (C) ) A total of 100 parts by mass of components) is preferably 0.01 to 12 parts by mass, and preferably 0.01 to 10 parts by mass. When the component (B) is used in such a range, better heat resistance and storage stability tend to be obtained.

(Thermosetting resin (C))
The resin composition of the present invention may further contain at least one thermosetting resin selected from an epoxy resin, a cyanate resin, and a maleimide compound as the component (C). The maleimide compound does not include the polyphenylene ether derivative (A).

  The epoxy resin is preferably an epoxy resin having two or more epoxy groups in one molecule. Here, the epoxy resin is classified into a glycidyl ether type epoxy resin, a glycidyl amine type epoxy resin, a glycidyl ester type epoxy resin, and the like. Among these, a glycidyl ether type epoxy resin may be selected.

  Epoxy resins are classified into various epoxy resins depending on the difference in the main skeleton. In each of the above types of epoxy resins, bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin are also included. Epoxy resin; alicyclic epoxy resin; aliphatic chain epoxy resin; phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F novolac type epoxy resin, etc .; phenol aralkyl Type epoxy resin; stilbene type epoxy resin; dicyclopentadiene type epoxy resin; naphthalene skeleton-containing type such as naphthol novolac type epoxy resin, naphthol aralkyl type epoxy resin It is classified into dicyclopentadiene type epoxy resin; epoxy resins; biphenyl type epoxy resins; biphenyl aralkyl type epoxy resins; xylylene-type epoxy resins; dihydroanthracene type epoxy resin.

  An epoxy resin may be used individually by 1 type, and may use 2 or more types together. Among these, naphthalene skeleton-containing epoxy resins and biphenyl aralkyl epoxy resins may be used from the viewpoints of high-frequency characteristics, heat resistance, glass transition temperature, thermal expansion coefficient, flame retardancy, and the like.

  Moreover, when using an epoxy resin as (C) component, the hardening | curing agent, hardening adjuvant, etc. of an epoxy resin can be used together as needed. These are not particularly limited, for example, polyamine compounds such as diethylenetriamine, triethylenetetramine, diaminodiphenylmethane, m-phenylenediamine, dicyandiamide; bisphenol A, phenol novolac resin, cresol novolac resin, bisphenol A novolac resin, phenol And polyphenol compounds such as aralkyl resins; acid anhydrides such as phthalic anhydride and pyromellitic anhydride; carboxylic acid compounds; and active ester compounds. These may be used alone or in combination of two or more. The amount used is not particularly limited and can be appropriately adjusted according to the purpose. Among these, from the viewpoints of heat resistance, glass transition temperature, thermal expansion coefficient, storage stability, and insulation reliability, it is preferable to use polyphenol compounds and active ester compounds.

  The cyanate resin is not particularly limited, and examples thereof include 2,2-bis (4-cyanatophenyl) propane, bis (4-cyanatophenyl) ethane, and bis (3,5-dimethyl-4-cyanato). Phenyl) methane, 2,2-bis (4-cyanatophenyl) -1,1,1,3,3,3-hexafluoropropane, α, α′-bis (4-cyanatophenyl) -m-diisopropyl Examples include benzene, a cyanate ester compound of a phenol-added dicyclopentadiene polymer, a phenol novolac-type cyanate ester compound, and a cresol novolac-type cyanate ester compound. Cyanate resin may be used individually by 1 type, and may use 2 or more types together. Among these, it is preferable to use 2,2-bis (4-cyanatophenyl) propane from the viewpoint of manufacturing cost and from the viewpoint of the overall balance of high-frequency characteristics and other characteristics.

  Moreover, when using cyanate resin as (C) component, the hardening | curing agent, hardening adjuvant, etc. of cyanate resin can be used together as needed. Although these are not specifically limited, For example, a monophenol compound, a polyphenol compound, an amine compound, an alcohol compound, an acid anhydride, a carboxylic acid compound etc. are mentioned. These may be used alone or in combination of two or more. The usage-amount of a hardening | curing agent and a hardening adjuvant is not restrict | limited in particular, According to the objective, it can adjust suitably. Among these, it is preferable to use a monophenol compound from the viewpoints of high-frequency characteristics, heat resistance, moisture absorption resistance, and storage stability.

  When using a monophenol compound, it is preferable to employ a method of pre-reacting and using it as a phenol-modified cyanate prepolymer from the viewpoint of solubility in an organic solvent. The monophenol compound to be used in combination may be blended in all of the prescribed amount when prepolymerized, or may be blended separately in the prescribed amount before and after prepolymerization, but from the viewpoint of storage stability, it is blended separately. Can be adopted.

  The maleimide compound is not particularly limited. For example, the maleimide compound (a) having at least two N-substituted maleimide structure-containing groups in the molecule [hereinafter sometimes referred to as component (a). And an amino bismaleimide compound (c) represented by the following general formula (VI) [Hereinafter, it may be referred to as component (c). ] Can be contained. From the viewpoints of solubility in an organic solvent, high frequency characteristics, adhesion to a conductor, and moldability of a prepreg, the maleimide compound is preferably an aminobismaleimide compound (c).

  The amino bismaleimide compound (c) is, for example, the component (a) and an aromatic diamine compound (b) having two primary amino groups in the molecule [hereinafter, referred to as component (b). Can be obtained by Michael addition reaction in an organic solvent.

(In the formula, A ⁴ is the same as the definition of A ^{1 in} the general formula (Z), and A ⁵ is a group represented by the following general formula (VII).)

(Wherein R ¹⁷ and R ¹⁸ 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. In the formula, A ⁸ is the number of carbon atoms. An alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, a sulfide group, a sulfonyl group, a carboxy group, a keto group, a fluorenylene group, a single bond, or the following general formula (VII-1) or (VII- 2) q ′ and r ′ are each independently an integer of 0 to 4.)

(In the formula, R ¹⁹ and R ²⁰ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. A ⁹ is an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, m- or a p-phenylenediisopropylidene group, an ether group, a sulfide group, a sulfonyl group, a carbooxy group, a keto group, or a single bond, and s ′ and t ′ are each independently an integer of 0 to 4.)

(Wherein R ²¹ is an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. A ¹⁰ and A ¹¹ are each independently an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, an ether group, A sulfide group, a sulfonyl group, a carbooxy group, a keto group, or a single bond, w is an integer of 0 to 4.)

C1-C5 aliphatic hydrocarbon group or halogen atom which R <^17> , R <^18> , R <^19> , R < ²⁰ > and R < ²¹ > in said general formula (VII), (VII-1) or (VII-2) represent As, R ¹ in the general formula (I) may be the same. The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and is preferably a methyl group or an ethyl group.

In the general formula (VII) or (VII-1), A ⁸ and A ⁹ represent an alkylene group having 1 to 5 carbon atoms and an alkylidene group having 2 to 5 carbon atoms, and in the general formula (VII-2). The alkylene group having 1 to 5 carbon atoms represented by A ¹⁰ and A ¹¹ is explained in the same manner as in the case of A ^{2 in} the general formula (III).

  q ′ and r ′ are integers of 0 to 4, and from the viewpoint of availability, both are preferably integers of 0 to 2, and preferably 0 or 2. s 'and t' are integers of 0 to 4, and from the viewpoint of availability, both are preferably integers of 0 to 2, preferably 0 or 1, and preferably 0. w is an integer of 0 to 4, and is preferably an integer of 0 to 2, and preferably 0 from the viewpoint of availability.

  The component (a) is not particularly limited, and for example, the same component as the bismaleimide compound (IX) may be applied. Examples of the component (a) 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-phenylene bismaleimide, m-phenylene bismaleimide, 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane, Bis (4-maleimidophenyl) sulfone, bis (4-maleimidophenyl) sulfide, bis (4-maleimidophenyl) ketone, 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane, bis (4- ( 4-maleimidophenoxy) phenyl) sulfone, 4,4′-bis (3-mer Imide phenoxy) biphenyl, 1,6-bismaleimide - (2,2,4-trimethyl) hexane and the like. (A) A component may be used individually by 1 type according to the objective, a use, etc., and may use 2 or more types together. The component (a) is preferably a bismaleimide compound, and is preferably bis (4-maleimidophenyl) methane from the viewpoint of being inexpensive, and has excellent dielectric properties and low water absorption. From the viewpoint of being, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide is preferable, and it has high adhesion to the conductor and mechanical properties (elongation, breaking strength, etc.). From the viewpoint of superiority, 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane is preferred.

  As described above, the amino bismaleimide compound (c) is a Michael addition reaction between the component (a) and the aromatic diamine compound (b) having two primary amino groups in the molecule in an organic solvent. Can be obtained.

  The component (b) is not particularly limited, but is 4,4′-diaminodiphenylmethane from the viewpoint of high solubility in an organic solvent, high reaction rate during synthesis, and high heat resistance. 4,4′-diamino-3,3′-dimethyl-diphenylmethane, 4,4′-diamino-3,3′-diethyl-diphenylmethane, 2,2-bis (4- (4-aminophenoxy) phenyl) propane 4,4 ′-[1,3-phenylenebis (1-methylethylidene)] bisaniline, 4,4 ′-[1,4-phenylenebis (1-methylethylidene)] bisaniline, and the like. In addition to excellent solubility, reaction rate and heat resistance, 4,4′-diaminodiphenylmethane, 4,4′-diamino-3,3′-dimethyl-diphenylmethane, 4,4 ′ from the viewpoint of being inexpensive. -Diamino-3,3'-diethyl-diphenylmethane is preferred. In addition to being excellent in solubility, reaction rate, and heat resistance, 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 preferable. Furthermore, in addition to excellent solubility, reaction rate, heat resistance, and adhesion to conductors, 4,4 ′-[1,3-phenylenebis (1- It is preferred to select methylethylidene)] bisaniline, 4,4 ′-[1,4-phenylenebis (1-methylethylidene)] bisaniline. These may be used alone or in combination of two or more according to the purpose and application.

  The organic solvent used for producing the amino bismaleimide compound (c) is not particularly limited, and for example, the organic solvent exemplified in the production process of the polyphenylene ether compound (A ″) can be applied. These may be used alone or in combination of two or more. Among these, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether, N, N-dimethylformamide, and N, N-dimethylacetamide are preferable from the viewpoint of solubility.

  The amounts used of the component (a) and the component (b) in the production of the component (c) are the -NH2 group equivalent (Ta2) of the component (b) and the maleimide group equivalent (Tb2) of the component (a). The equivalent ratio (Tb2 / Ta2) is preferably in the range of 1 to 10, and preferably in the range of 2 to 10. By using the component (a) and the component (b) within the above range, in the resin composition, prepreg and laminate of the present invention, excellent high frequency characteristics, high adhesion to a conductor, excellent heat resistance, high Glass transition temperature and high flame retardancy are obtained.

  In the Michael addition reaction for producing the amino bismaleimide compound (c), it is not necessary to use a reaction catalyst, but it can also be used as necessary. Although it does not restrict | limit especially as a reaction catalyst, The reaction catalyst which can be used for the Michael addition reaction at the time of manufacture of said polyphenylene ether derivative (A) is applicable. The blending amount of the reaction catalyst is not particularly limited as described above.

  Moreover, when using a maleimide compound as (C) component, the hardening | curing agent of a maleimide compound, a crosslinking agent, a hardening adjuvant, etc. can be used together. These are not particularly limited, for example, vinyl compounds such as styrene monomer, divinylbenzene and divinylbiphenyl; (meth) acrylate compounds; allyl compounds such as triallyl cyanurate and triallyl isocyanurate; diaminodiphenylmethane and the like And the polyamine compounds. These may be used alone or in combination of two or more. These usage amounts are not particularly limited, and can be appropriately adjusted according to the purpose. Among these, a vinyl compound and a polyamine compound may be used from the viewpoint of high frequency characteristics and heat resistance.

  The amino bismaleimide compound (c) is obtained by charging a predetermined amount of the above component (a), component (b), an organic solvent and, if necessary, a reaction catalyst into a reactor and subjecting it to a Michael addition reaction while heating, keeping warm, and stirring. . As the reaction conditions such as the reaction temperature and reaction time in this step, for example, the reaction conditions during the Michael addition reaction during the production of the polyphenylene ether derivative (A) described above can be applied.

  The reaction concentration (solid content concentration) is not particularly limited, but is preferably 10 to 90% by mass, and preferably 20 to 80% by mass. When the reaction concentration is 10% by mass or more, the reaction rate does not become too slow and tends to be more advantageous in terms of production cost. In the case of 90% by mass or less, better solubility tends to be obtained. Moreover, since the solution viscosity is low, the stirring efficiency is good and gelation is rare. In addition, after the production of the amino bismaleimide compound (c), as in the production of the polyphenylene ether derivative (A), part or all of the organic solvent is removed (concentrated) according to the purpose, or an organic solvent is added. And can be diluted.

(Content ratio of (A) component and (C) component)
The content ratio [(A) :( C)] of the component (A) and the component (C) is not particularly limited, but is preferably 5:95 to 80:20 by mass ratio. ~ 75: 25 is preferred, 5:95 to 70:30 is preferred, 20:80 to 60:40 is preferred, and 20:80 to 50:50 is preferred. If the content ratio of the component (A) with respect to the total amount of the component (A) and the component (C) is 5% by mass or more, more excellent high frequency characteristics and low hygroscopicity tend to be obtained. Moreover, if it is 80 mass% or less, it exists in the tendency for the more excellent heat resistance, the more excellent moldability, and the more excellent workability to be obtained.

The thermosetting resin composition of the present invention optionally comprises an inorganic filler (D) (hereinafter may be referred to as (D) component), a flame retardant (E) (hereinafter referred to as (E) component). May be used). By including these, various properties when the laminate is obtained can be further improved. For example, low thermal expansion characteristics, high elastic modulus, heat resistance, flame retardancy, and the like can be improved by arbitrarily including an appropriate inorganic filler in the thermosetting resin composition of the present invention. Moreover, high flame retardance can be provided, suppressing the fall of a high frequency characteristic, heat resistance, adhesiveness with a conductor, and a glass transition temperature by containing a suitable flame retardant.

The component (D) used in the thermosetting resin composition of the present invention is not particularly limited. For example, silica, alumina, titanium oxide, mica, beryllia, barium titanate, potassium titanate, titanium Strontium acid, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, calcined clay, etc., talc, aluminum borate Aluminum borate, silicon carbide and the like can be used. These may be used alone or in combination of two or more. Moreover, there is no restriction | limiting in particular about the shape and particle size of an inorganic filler, For example, a particle size of 0.01-20 micrometers, Preferably 0.1-10 micrometers is used suitably. Here, the particle size refers to the average particle size, and when the cumulative frequency distribution curve by the particle size is determined with the total volume of the particles being 100%, the volume is 50
The particle diameter at a point corresponding to%. It can be measured by a particle size distribution measuring apparatus using a laser diffraction scattering method.

When the component (D) is used, the amount used is not particularly limited. For example, the content ratio of the component (D) in the thermosetting resin composition containing the component (D) is 3 to 65% by volume. It is preferable that it is 5-60 volume%. When the content ratio of the component (D) in the entire thermosetting resin composition is in the above range, good curability, moldability, and chemical resistance can be obtained. Moreover, when using (D) component, it is preferable to use a coupling agent together in order to improve the dispersibility of (D) component and the adhesiveness of (D) component and the organic component in a resin composition. The coupling agent is not particularly limited, and for example, various silane coupling agents and titanate coupling agents can be used. These may be used alone or in combination of two or more. Moreover, the usage-amount is not specifically limited, It is preferable to set it as 0.1-5 mass parts with respect to 100 mass parts of (D) component to be used, and it shall be 0.5-3 mass parts. More preferred. If it is this range, there will be little fall of various characteristics and the feature by use of said (D) component can be exhibited effectively. When using a coupling agent, the component (D) is added to the resin composition, and then the coupling agent is added. Or the system which uses the inorganic filler surface-treated by the wet method is preferable. By using this method, the characteristics of the component (D) can be expressed more effectively.

In the present invention, when the component (D) is used, a slurry in which the component (D) is dispersed in an organic solvent in advance for the purpose of improving the dispersibility of the component (D) in the thermosetting resin composition. It is more preferable to use as. The organic solvent used when slurrying the component (D) is not particularly limited, but the organic solvents exemplified in the production process of the polyphenylene ether compound (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,
Cyclohexanone is preferred from the viewpoint of dispersibility. Further, the nonvolatile content concentration of the slurry is not particularly limited, but for example, 50 to 80% by mass is preferable and 60 to 80% by mass is more preferable from the viewpoint of sedimentation and dispersibility of the inorganic filler.

(Flame retardant (E))
The resin composition of the present invention may contain a flame retardant (E).

  Examples of the component (E) include phosphorus flame retardants, metal hydrates, and halogen flame retardants. The component (E) is preferably a phosphorus flame retardant and a metal hydrate from the viewpoint of environmental problems. A flame retardant (E) may be used individually by 1 type, and may use 2 or more types together.

-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 is preferably an inorganic phosphorus-based flame retardant. A phosphorus-based flame retardant is preferable. From the viewpoint of environmental problems, it is possible to select one that does not contain a halogen atom. From the viewpoint of high-frequency characteristics, adhesion to conductors, heat resistance, glass transition temperature, thermal expansion coefficient, and flame retardancy, an organic phosphorus flame retardant is preferable.

  Examples of inorganic phosphorus 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 phosphate amides Phosphoric acid; phosphine oxide and the like.

  Examples of organic phosphorus flame retardants include aromatic phosphoric acid esters, monosubstituted phosphonic acid diesters, disubstituted phosphinic acid esters, disubstituted phosphinic acid metal salts, organic nitrogenous phosphorus compounds, and cyclic organic phosphorus compounds. Is mentioned. Among these, an aromatic phosphate compound and a metal salt of a disubstituted phosphinic acid can be selected. Here, the metal salt is preferably 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, and preferably an aluminum salt. Among organic phosphorus flame retardants, an aromatic phosphate ester can be selected.

  Examples of the aromatic phosphate ester include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl di-2,6-xylenyl phosphate, resorcinol bis (diphenyl phosphate), 1,3 -Phenylenebis (di-2,6-xylenyl phosphate), bisphenol A-bis (diphenyl phosphate), 1,3-phenylenebis (diphenyl phosphate) and the like.

  Examples of monosubstituted phosphonic acid diesters include divinyl phenylphosphonate, diallyl phenylphosphonate, and bis (1-butenyl) phenylphosphonate.

  Examples of the disubstituted 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, and a metal salt of diarylphosphinic acid. These metal salts are preferably lithium salt, sodium salt, potassium salt, calcium salt, magnesium salt, aluminum salt, titanium salt, or zinc salt, and an aluminum salt may be selected.

  Examples of the organic nitrogen-containing phosphorus compound include phosphazene compounds such as bis (2-allylphenoxy) phosphazene and dicresyl phosphazene; melamine phosphate; melamine pyrophosphate; melamine polyphosphate; melam polyphosphate.

  As the cyclic organic phosphorus compound, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-10- And phosphaphenanthrene-10-oxide.

  Among these, it is preferably at least one selected from an aromatic phosphate ester, a metal salt of a disubstituted phosphinic acid, and a cyclic organophosphorus compound, and selected from a metal salt of a disubstituted phosphinic acid and a cyclic organophosphorus compound. At least one kind is preferable, and a metal salt of a disubstituted phosphinic acid and a cyclic organophosphorus compound may be used in combination. In particular, the metal salt of disubstituted phosphinic acid is preferably a metal salt of dialkylphosphinic acid, and is preferably an aluminum salt of dialkylphosphinic acid. The cyclic organophosphorus compound is preferably 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.

  When the metal salt of disubstituted phosphinic acid and the cyclic organic phosphorus compound are used in combination, the content ratio of the metal salt of disubstituted phosphinic acid to the cyclic organic phosphorus compound [metal salt of disubstituted phosphinic acid / cyclic organic phosphorus compound] is: The mass ratio is preferably 0.6 to 2.5, preferably 0.9 to 2, preferably 1 to 2, and preferably 1.2 to 2.

  The aromatic phosphate is preferably an aromatic phosphate represented by the following general formula (F-1) or (F-2), and the metal salt of the disubstituted phosphinic acid is: A metal salt of a disubstituted phosphinic acid represented by the general formula (F-3) is preferable.

(Wherein R ^{F1 to} R ^F5 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. E and f are each independently an integer of 0 to 5, g, h and I is an integer of 0-4 each independently.

R ^F6 and R ^F7 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. m is an integer of 1-4. )

Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R ^{F1 to} R ^F5 include the same as those in the case of R ^{1 in} the general formula (I).

  e and f are preferably integers of 0 to 2, and are preferably 2. g, h and I are preferably integers of 0 to 2, preferably 0 or 1, and preferably 0.

Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R ^F6 and R ^F7 include the same as those in the case of R ^{1 in} the general formula (I). The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and more preferably an ethyl group.

Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms represented by R ^F6 and R ^F7 include a phenyl group, a naphthyl group, a biphenylyl group, and an anthryl group. The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms.

  m represents the valence of the metal ion, that is, changes within a range of 1 to 4 corresponding to the type of M.

  M is preferably an aluminum atom. Note that m is 3 when M is an aluminum atom.

-Metal hydrate-
Examples of metal hydrates include aluminum hydroxide hydrate, magnesium hydroxide hydrate, and the like. These may be used alone or in combination of two or more. The metal hydroxide may correspond to an inorganic filler, but is classified as a flame retardant in the case of a material that can impart flame retardancy.

-Halogen flame retardant-
Examples of the halogen flame retardant include a chlorine flame retardant and a bromine flame retardant. Examples of the chlorinated flame retardant include chlorinated paraffin. Examples of brominated flame retardants include brominated epoxy resins such as brominated bisphenol A type epoxy resins and brominated phenol novolac type epoxy resins; 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 flame retardants such as 4,6-tris (tribromophenoxy) -1,3,5-triazine (here, “added type” refers to a polymer in a form in which bromine is not chemically bonded) Introduced, that is, blended.); Brominated reactive flame retardants containing unsaturated double bond groups such as bromophenylmaleimide, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromobisphenol A type dimethacrylate, pentabromobenzyl acrylate, brominated styrene (where, “Reactive type” refers to a polymer in which bromine is introduced into a polymer in a chemically bonded form. These may be used alone or in combination of two or more.

(Content of component (E))
When a phosphorus flame retardant is used as the component (E), the content of the phosphorus flame retardant in the resin composition of the present invention is not particularly limited. For example, the resin composition in terms of solid content (the above (D ) The total content of other components excluding the component is preferably 0.2 to 5% by mass, more preferably 0.3 to 3% by mass. When the phosphorus atom content is 0.2% by mass or more, better flame retardancy tends to be obtained. Moreover, when content of a phosphorus atom is 5 mass% or less, it exists in the tendency for better moldability, the high adhesiveness with a conductor, the outstanding heat resistance, and a high glass transition temperature.

  On the other hand, when the halogen-based flame retardant is contained in the resin composition of the present invention, from the viewpoint of environmental problems and chemical resistance, the total of 100 parts by mass of the component (A) and the component (C) (however, the component (C) When not used, it is preferably 20 parts by mass or less, preferably 10 parts by mass or less, and preferably 5 parts by mass or less, with respect to (100 parts by mass of component (A)).

  Further, when the resin composition of the present invention contains a flame retardant other than the phosphorus-based flame retardant and the halogen-based flame retardant, it is not particularly limited, but the total of 100 parts by mass of the component (A) and the component (C) (However, when not using (C) component, it is preferable that it is 0.5-20 mass parts with respect to (A) component 100 mass parts), and it is preferable that it is 1-15 mass parts, It is preferably 10 parts by mass, and preferably 1 to 6 parts by mass.

(Flame retardant aid)
The resin composition of the present invention can contain a flame retardant aid. As the flame retardant aid, for example, an inorganic flame retardant aid such as antimony trioxide or zinc molybdate can be used.

  When the flame retardant aid is contained in the resin composition of the present invention, the content ratio is not particularly limited. For example, the total of 100 parts by mass of (A) component and (C) component (however, (C When the component is not used, it is preferably 0.1 to 20 parts by mass, and preferably 0.1 to 10 parts by mass with respect to (A) component 100 parts by mass). When the flame retardant aid is used in such a range, better chemical resistance tends to be obtained.

  The resin composition of the present invention includes, as necessary, resin materials such as known thermoplastic resins and elastomers, as well as coupling agents, antioxidants, thermal stabilizers, antistatic agents, ultraviolet absorbers, and pigments. In addition, a colorant, a lubricant and the like can be appropriately selected and contained. These may be used alone or in combination of two or more. Moreover, these usage-amounts are not specifically limited.

(Organic solvent)
The resin composition of the present invention may contain an organic solvent from the viewpoint of facilitating handling by dilution and easy manufacture of a prepreg described later.

  Examples of the organic solvent include, but are not limited to, alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; tetrahydrofuran Ether solvents such as toluene; xylene, mesitylene and other aromatic solvents; dimethylformamide, dimethylacetamide, N-methylpyrrolidone and other nitrogen atom containing solvents; dimethyl sulfoxide and other sulfur atom containing solvents; γ-butyrolactone and other esters System solvents and the like.

  Among these, an alcohol solvent, a ketone solvent, and a nitrogen atom-containing solvent are preferable from the viewpoint of solubility.

  One organic solvent may be used alone, or two or more organic solvents may be used in combination.

  Although there is no restriction | limiting in particular in content of the organic solvent in the resin composition of this invention, it is preferable that solid content concentration is 30-90 mass%, and it is preferable that it is 40-80 mass%. By using a resin composition having a solid content concentration within the above range, the handleability becomes easy, the impregnation property to the base material and the appearance of the produced prepreg are good, and the resin solids in the prepreg described later Adjustment of the partial concentration is facilitated, and production of a prepreg having a desired thickness tends to be facilitated.

  The resin composition of the present invention can be obtained by mixing the component (A) and the component (B), the component (C), other components, an organic solvent, etc., which are used as necessary, by a known method. it can. At this time, it may be dissolved or dispersed while stirring. Conditions such as mixing order, temperature and time during mixing and stirring are not particularly limited and can be arbitrarily set.

  The glass transition temperature of the cured product of the resin composition when the laminate is produced from the resin composition of the present invention is not particularly limited, but when manufacturing good heat resistance and through-hole connection reliability, electronic parts, etc. From the viewpoint of excellent workability, the glass transition temperature after curing is preferably 180 ° C. or higher, more preferably 200 ° C. or higher, at 200 ° C. or higher for 60 minutes or longer. The upper limit of the glass transition temperature is not particularly limited, but is preferably, for example, 1000 ° C. or less, preferably 500 ° C. or less, and preferably 300 ° C. or less.

  Moreover, the thermal expansion coefficient (Z direction, Tg or less) of the cured product of the resin composition when producing a laminate from the resin composition of the present invention is not particularly limited, but from the viewpoint of suppressing warpage of the laminate, It is preferably 45 ppm / ° C. or less, more preferably 43 ppm / ° C. or less. Although there is no restriction | limiting in the lower limit of a thermal expansion coefficient, For example, it is 25 ppm / degrees C or more.

  The glass transition temperature and the thermal expansion coefficient are values measured in accordance with the IPC standard as described in the examples.

  The dielectric constant and dielectric loss tangent of the cured product of the resin composition when a laminate is produced from the resin composition of the present invention is not particularly limited, but from the viewpoint of being suitably used in a high frequency band, the dielectric constant at 10 GHz is small. Is preferably 3.8 or less, more preferably 3.7 or less, and still more preferably 3.6 or less. The lower limit of the dielectric constant is not particularly limited but is, for example, 0.5 or more.

  The dielectric loss tangent is preferably small, and the dielectric loss tangent at 10 GHz is preferably 0.006 or less, and more preferably 0.0055 or less. The lower limit of the dielectric loss tangent is not particularly limited and may be as small as possible. For example, it is 0.0001 or more.

  The dielectric constant and dielectric loss tangent are values measured by the cavity resonator method as in the examples.

[Prepreg]
The present invention also provides a prepreg having the resin composition of the present invention and a sheet-like fiber reinforced base material. That is, the prepreg according to the present invention is formed using the resin composition of the present invention and a sheet-like fiber reinforced base material. The prepreg can be obtained, for example, by impregnating or applying the resin composition of the present invention to a sheet-like fiber reinforced substrate and drying it. More specifically, for example, the prepreg of the present invention can be produced by heating and drying in a drying furnace usually at a temperature of 80 to 200 ° C. for 1 to 30 minutes and semi-curing (B-stage). . The usage-amount of a resin composition can be determined so that the solid content density | concentration derived from the resin composition in the prepreg after drying may be 30-90 mass%. When the solid content concentration is within the above range, when a laminate is obtained, better formability tends to be obtained.

  As the sheet-like fiber reinforced base material of the prepreg, known materials used for various types of laminates for electrical insulating materials are used. Examples of the material for the sheet-like reinforcing substrate include inorganic fibers such as E glass, D glass, S glass, and Q glass; organic fibers such as polyimide, polyester, and tetrafluoroethylene; and mixtures thereof. These sheet-like reinforcement base materials have shapes, such as a woven fabric, a nonwoven fabric, a robink, a chopped strand mat, a surfacing mat, for example. Moreover, the thickness in particular of a sheet-like fiber reinforcement base material is not restrict | limited, For example, a 0.02-0.5 mm thing can be used. Also, those surface-treated with a coupling agent or the like and mechanically subjected to fiber opening treatment are suitable from the viewpoint of impregnation of the resin composition, heat resistance when made into a laminate, moisture absorption resistance and workability. Can be used for

  As a method for impregnating or applying the resin composition to the sheet-like reinforcing substrate, for example, the following hot melt method or solvent method can be employed.

  In the hot melt method, an organic solvent is not contained in the resin composition, and (1) a method of once coating a coated paper having good releasability from the composition and laminating it on a sheet-like reinforcing substrate or (2 ) It is a method of coating directly on a sheet-like reinforcing substrate with a die coater.

  On the other hand, in the solvent method, the resin composition contains an organic solvent, the sheet-like reinforcing base material is immersed in the obtained resin composition, the resin composition is impregnated into the sheet-like reinforcing base material, and then dried. Is the method.

[Laminated boards and multilayer printed wiring boards]
The laminate of the present invention has the prepreg of the present invention and a genus foil. That is, the laminate of the present invention is formed using the prepreg of the present invention and the metal foil. The laminated plate of the present invention has, for example, a metal plate disposed on one or both surfaces of one prepreg of the present invention, or a metal foil disposed on one or both surfaces of a prepreg obtained by stacking two or more prepregs of the present invention. Then, it can be obtained by heating and pressing.

  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 is preferable, copper and aluminum are preferable, and copper is preferable.

  The conditions for heat and pressure molding are not particularly limited. For example, the temperature may be 100 to 300 ° C., the pressure may be 0.2 to 10.0 MPa, and the time may be 0.1 to 5 hours. it can. Moreover, the heat press molding can employ | adopt the method of hold | maintaining a vacuum state for 0.5 to 5 hours using a vacuum press etc. FIG.

  Moreover, the multilayer printed wiring board of this invention has the prepreg or laminated board of this invention. That is, the multilayer printed wiring board of the present invention is formed by heating and pressing the prepreg or laminated board of the present invention. The conditions for heat and pressure molding are not particularly limited, and the same conditions as described above can be adopted. The multilayer printed wiring board of the present invention can be subjected to circuit formation processing and multilayer adhesion processing by a known method using, for example, the prepreg or laminate of the present invention by a known method. It can be manufactured by doing.

  The resin composition, prepreg, laminated board and multilayer printed wiring board of the present invention can be suitably used for electronic equipment that handles high frequency signals of 1 GHz or higher, and particularly those that handle high frequency signals of 10 GHz or higher or high frequency signals of 30 GHz or higher. It can use suitably for an apparatus.

  The preferred embodiments of the present invention have been described above, but these are examples for explaining the present invention, and the scope of the present invention is not intended to be limited to these embodiments.

  The present invention can be implemented in various modes different from the above-described embodiments without departing from the gist thereof.

  Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples.

[Production of polyphenylene ether derivative (A)]
The polyphenylene ether derivative (A) was produced according to the following procedure and the blending amount shown in Table 1.

(Production Example A-1: Production of polyphenylene ether derivative (A-1))
Toluene, polyphenylene ether having a number average molecular weight of about 16000 and p-aminophenol are charged into a 2 L glass flask container equipped with a thermometer, a reflux condenser, and a stirrer, which can be heated and cooled, and stirred at 90 ° C. While dissolving.

  After visually confirming dissolution, t-butylperoxyisopropyl monocarbonate and manganese naphthenate were added, reacted at a solution temperature of 90 ° C. for 4 hours, then cooled to 70 ° C. and having a primary amino group at the molecular end. A polyphenylene ether compound (A ″) was obtained.

  A small amount of this reaction solution was taken out and measured by gel permeation chromatography (GPC). As a result, the peak derived from p-aminophenol disappeared, and the number average molecular weight of the polyphenylene ether compound (A ″) was about 9200. When a small amount of the reaction solution taken out was dropped into a methanol / benzene mixed solvent (mixing mass ratio: 1: 1) and reprecipitated and subjected to FT-IR measurement of the purified solid content (reaction product), 3400 cm- The appearance of a peak derived from a primary amino group in the vicinity of 1 was confirmed.

Here, the number average molecular weight was converted from a calibration curve using standard polystyrene by gel permeation chromatography (GPC). The calibration curve is standard polystyrene: TSK standard POLYSTYRENE (Type; A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) [manufactured by Tosoh Corporation, The product name] was used to approximate the cubic equation. The measurement conditions for GPC are shown below.
apparatus:
Pump: L-6200 [manufactured by Hitachi High-Technologies Corporation]
Detector: L-3300 RI [manufactured by Hitachi High-Technologies Corporation]
Column oven: L-655A-52 [manufactured by Hitachi High-Technologies Corporation]
Column: Guard column; TSK Guardcolumn HHR-L + column; TSKgel G4000HHR + TSKgel G2000HHR [all trade names, manufactured by Tosoh Corporation]
Column size: 6.0 × 40 mm (guard column), 7.8 × 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

  Next, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide and propylene glycol monomethyl ether are added to the reaction solution, and the liquid temperature is raised while stirring. After reacting for 4 hours while keeping the temperature at 0 ° C., the mixture was cooled and then filtered through a 200 mesh filter to produce a polyphenylene ether derivative (A-1).

  A small amount of this reaction solution was taken out, reprecipitated in the same manner as described above, and subjected to FT-IR measurement of the purified solid. The disappearance of the primary amino group-derived peak around 3400 cm −1 and the carbonyl of maleimide at 1700 to 1730 cm −1. The appearance of group-derived peaks was confirmed. Moreover, when GPC (same conditions as the above) of this solid substance was measured, the number average molecular weight was about 9400.

(Production Examples A-2 to A-3: Production of polyphenylene ether derivatives (A-2) to (A-3))
In Production Example A-1, polyphenylene ether derivatives (A-2) to (A-3) are produced in the same manner as in Production Example A-1, except that each raw material and blending amount are changed as shown in Table 1. did. Table 1 shows the number average molecular weights of the polyphenylene ether derivatives (A-2) to (A-3).

[Production of low molecular weight polyphenylene ether]
Low molecular weight polyphenylene ether (R-1 to 2), which is a comparative material, was produced according to the following procedure and the blending amount in Table 2.

(Comparative Production Example R-1: Production of Low Molecular Weight Polyphenylene Ether (R-1))
Toluene, polyphenylene ether having a number average molecular weight of about 16000, and bisphenol A were charged into a glass flask container with a capacity of 2 liters that was equipped with a thermometer, a reflux condenser, and a stirrer. The liquid temperature was kept at 80 ° C. and stirred and dissolved. After confirming dissolution visually, t-butyl peroxyisopropyl monocarbonate and cobalt naphthenate were blended and reacted for 1 hour to obtain low molecular weight polyphenylene ether (R-1). It was about 8000 when GPC (polystyrene conversion, eluent: tetrahydrofuran) of this low molecular weight polyphenylene ether (R-1) was measured.

(Comparative Production Example R-2: Production of Low Molecular Weight Polyphenylene Ether (R-2))
250 parts by mass of toluene (organic solvent A), 100 parts by mass of polyphenylene ether having a number average molecular weight of about 16000, 3.8 parts by mass of bisphenol A, 2.9 parts by mass of t-butylperoxyisopropyl monocarbonate, and 0.027 of cobalt naphthenate A low molecular weight polyphenylene ether solution was obtained in the same manner as in Comparative Production Example R-1, except for the blending amount. A large amount of methanol was added to this solution to reprecipitate the low molecular weight polyphenylene ether, followed by drying at 80 ° C./3 hours under reduced pressure to remove the organic solvent A to obtain a solid low molecular weight polyphenylene ether (R-2 ′). Got. Next, the low molecular weight polyphenylene ether (R-2 ′), chloromethylstyrene, tetra-n-butylammonium bromide, toluene (organic solvent B) were heated with a thermometer, a reflux condenser, a stirrer, and a dropping funnel. It was put into a glass flask container having a capacity of 2 liters that can be cooled. After keeping the liquid temperature at 75 ° C. and stirring and dissolving, an aqueous sodium hydroxide solution was dropped into this solution over 20 minutes, and the mixture was further stirred and reacted at 75 ° C. for 4 hours. Next, the flask contents were neutralized with a 10% aqueous hydrochloric acid solution, and a large amount of methanol was added for reprecipitation, followed by filtration. The filtrate was washed three times with a mixture of methanol 80 and water 20 and then dried under reduced pressure at 80 ° C. for 3 hours to obtain a low molecular weight polyphenylene ether (R-2) having an ethenylbenzylated end. . It was about 3000 when GPC (polystyrene conversion, eluent: tetrahydrofuran) of this low molecular weight polyphenylene ether (R-2) was measured.

[Production of polyphenylene ether-modified butadiene prepolymer]
A polyphenylene ether-modified butadiene prepolymer (R-3) as a comparative material was produced according to the following procedure and the blending amount in Table 2.

(Comparative Production Example R-3: Production of polyphenylene ether-modified butadiene prepolymer (R-3))
To a glass flask container with a capacity of 2 liters, which is equipped with a thermometer, a reflux condenser, a vacuum concentrator, and a stirrer, is charged toluene and polyphenylene ether having a number average molecular weight of about 16000, and the temperature inside the flask Was set at 90 ° C. and dissolved by stirring. Next, polybutadiene resin and bis (4-maleimidophenyl) methane were added, stirred and dissolved. After the liquid temperature was set to 110 ° C., 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane was blended as a reaction initiator and reacted for 1 hour with stirring to obtain polyphenylene ether. Butadiene resin and bismaleimide were pre-reacted in the presence of. Furthermore, after setting the liquid temperature to 80 ° C., the solution was concentrated under reduced pressure so that the solid content concentration of the solution was 45% by mass with stirring, and then cooled to obtain a polyphenylene ether-modified butadiene prepolymer solution of Comparative Production Example R-3. . Conversion rate of bis (4-maleimidophenyl) methane in this polyphenylene ether-modified butadiene prepolymer (R-3) solution (value obtained by subtracting the unconverted content (measured value) of bis (4-maleimidophenyl) methane from 100) Was 30% when measured by GPC (polystyrene conversion, eluent: tetrahydrofuran).

“Organic solvent A” and “organic solvent B” are obtained by dividing each organic solvent for convenience by the difference in charging timing in Production Example R-2, and there is no difference as a component.

[Production of amino bismaleimide compounds (C-1) to (C-3) and a phenol-modified cyanate prepolymer (C-4)]
According to the following procedure and the compounding amount of Table 3, amino bismaleimide compounds (C-1) to (C-3) and a phenol-modified cyanate prepolymer (C-4) which are thermosetting resins were produced.

(Production Example B-1: Production of amino bismaleimide compound (C-1))
A 2-L (4- (4-maleimidophenoxy) phenyl) propane, 2,2-bis (2,2-bis (4- (4-maleimidophenoxy) phenyl) propane was added to a 1 L glass flask container capable of heating and cooling equipped with a thermometer, a reflux condenser, and a stirring device. 4- (4-Aminophenoxy) phenyl) propane and propylene glycol monomethyl ether were added, and the mixture was allowed to react with stirring for 3 hours while maintaining the liquid temperature at 120 ° C., then cooled and filtered through a 200 mesh filter. As a result, an amino bismaleimide compound (C-1) was produced.

(Production Examples C-2 to C-3: Production of amino bismaleimide compounds (C-2) to (C-3)) In Production Example C-1, each raw material and its blending amount were changed as shown in Table 3. Except that, amino bismaleimide compounds (C-2) to (C-3) were produced in the same manner as in Production Example C-1.

(Production Example C-4: Production of Phenol-modified Cyanate Prepolymer (B-4)) To a 1 L glass flask container with a thermometer, a reflux condenser, and a stirrer capable of heating and cooling, toluene, 2, 2-bis (4-cyanatophenyl) propane and p- (α-cumyl) phenol were added, and after confirming that they were dissolved, the reaction temperature was kept at 110 ° C. while stirring, as a reaction catalyst. Zinc naphthenate was added and reacted for 3 hours. Thereafter, the mixture was cooled and then filtered through a 200 mesh filter to produce a phenol-modified cyanate prepolymer (C-4).

Abbreviations of each material in Tables 1 to 3 are as follows.
(1) Polyphenylene ether / PPO640: Polyphenylene ether (manufactured by SABIC Innovative Plastics), number average molecular weight = about 16000, trade name (2) aminophenol compound (VIII) and phenol compound / p-aminophenol: Ihara Chemical Industrial Co., Ltd. Company-made m-aminophenol: Ihara Chemical Industry Co., Ltd. Bisphenol A: Bisphenol A, 2,2'-bis (4-hydroxyphenyl) propane, Mitsubishi Chemical Co., Ltd. (3) bismaleimide compound (IX) and Maleimide compound (a)
BMI-5100: 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide, trade name (manufactured by Daiwa Kasei Kogyo Co., Ltd.)
BMI-4000: 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane, trade name (manufactured by Daiwa Kasei Kogyo Co., Ltd.)
BMI-TMH: 1,6-bismaleimide- (2,2,4-trimethyl) hexane, trade name (manufactured by Daiwa Kasei Kogyo Co., Ltd.)
BMI-1000: bis (4-maleimidophenyl) methane (manufactured by Daiwa Kasei Kogyo Co., Ltd.)
(4) Reaction catalyst perbutyl (registered trademark) I: t-butylperoxyisopropyl monocarbonate (manufactured by NOF Corporation)
Perhexa (registered trademark) TMH: 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane (manufactured by NOF Corporation)
Manganese naphthenate: Wako Pure Chemical Industries, Ltd. Cobalt naphthenate: Wako Pure Chemical Industries, Ltd. Zinc naphthenate: Wako Pure Chemical Industries, Ltd. (5) Polybutadiene resin B-3000: Butadiene homopolymer ( Number average molecular weight: about 3000, manufactured by Nippon Soda Co., Ltd.)
(6) Aromatic diamine compound (b)
BAPP: 2,2-bis (4- (4-aminophenoxy) phenyl) propane, trade name (manufactured by Wakayama Seika Kogyo Co., Ltd.)
Bisaniline-P: 4,4 ′-[1,4-phenylenebis (1-methylethylidene)] bisaniline, trade name (manufactured by Mitsui Chemicals, Inc.)
Bisaniline-M: 4,4 ′-[1,3-phenylenebis (1-methylethylidene)] bisaniline, trade name (manufactured by Mitsui Chemicals, Inc.)
(7) Cyanate resin / BADCy: Primaset (registered trademark) BADCy, 2,2-bis (4-cyanatophenyl) propane, trade name (manufactured by Lonza)
(8) Monophenol compound / p- (α-cumyl) phenol: manufactured by Mitsui Chemicals Fine Co., Ltd. (9) Other compounds / chloromethylstyrene: p-chloromethylstyrene / m-chloromethylstyrene ratio = 50/50 (Tokyo) (Made by Kasei Kogyo Co., Ltd.)
Tetra-n-butylammonium bromide: manufactured by Tokyo Chemical Industry Co., Ltd. 50% NaOH solution: manufactured by Wako Pure Chemical Industries, Ltd.

[Examples 1-22, Comparative Examples 1-7; Preparation of Resin Composition]
Stir and mix each component described in Table 4 and Table 5 with heating at room temperature or 50 to 80 ° C. according to the blending amount (unit: parts by mass) described in Table 4 and Table 5 to obtain a solid content (nonvolatile content). A resin composition having a concentration of 40 to 60% by mass was prepared.

Here, as the blending amount of the inorganic filler, the density of the resin composition (excluding the inorganic filler) is usually 1.20 to 1.25 g / cm ³ , and the density of the used inorganic filler is 2. 2 to 3.01 g / cm ³ .
Note that the raw materials and intermediate products used in the above production examples are extremely small or inactivated, and can be ignored even if they remain in the resin composition.

[Evaluation / Measurement Method]
Each measurement and evaluation was performed according to the following method using the resin compositions obtained in the above Examples and Comparative Examples. The results are shown in Tables 6-8. The results of Examples 1 to 22 and Comparative Examples 1 to 7 in Tables 6 to 8 are the measurements and evaluations of the compositions prepared in Adjustment Examples 1 to 22 and Comparative Adjustment Examples 1 to 7 in Tables 4 and 5, respectively. It is a result.

(Preparation of prepreg and copper clad laminate)
The resin composition obtained in each example was applied to a glass cloth (E glass, manufactured by Nitto Boseki Co., Ltd.) having a thickness of 0.1 mm, and then dried by heating at 160 ° C. for 7 minutes to obtain a resin content (resin content). ) About 54% by mass of a prepreg was produced. These 6 prepregs are stacked, and on the top and bottom thereof, a low profile copper foil (FV-WS, M surface Rz: 1.5 μm, manufactured by Furukawa Electric Co., Ltd.) having a thickness of 18 μm is arranged so that the M surface is in contact with it. A double-sided copper-clad laminate (thickness: 0.8 mm) was produced by heating and pressing under conditions of a temperature of 230 ° C., a pressure of 3.9 MPa, and a time of 180 minutes.

(Appearance evaluation of prepreg)
The appearance of the prepreg obtained above was observed. Appearance was evaluated by visual inspection, and the surface of the prepreg had some unevenness, streaks, foaming, and phase separation, and those with poor surface smoothness were marked with ×, and those with no appearance abnormalities were marked with ○. .

(Characteristic evaluation of copper clad laminate)
The copper clad laminate obtained above was evaluated for formability, dielectric properties, copper foil peel strength, glass transition temperature, thermal expansion coefficient, solder heat resistance and flame retardancy. The characteristic evaluation method of the copper clad laminate is as follows.

(1) Formability The formability was evaluated by observing the appearance of the laminated board obtained by etching the copper foils on both sides. The moldability was evaluated by visual inspection, and any of unevenness, streaks, blurring, and voids was observed.
(2) Dielectric properties Dielectric properties (relative dielectric constant, dielectric loss tangent) are test pieces obtained by removing the copper foils on both sides by etching, cutting to a size of 60 mm × 2 mm, and drying at 105 ° C./1 h. And Dk and Df at 10 GHz were calculated from the resonance frequency obtained by the cavity resonator method and the unloaded Q value.

The measurement was performed at an ambient temperature of 25 ° C. using a vector network analyzer E8364B manufactured by Agilent Technologies, CP531 (10 GHz resonator) manufactured by Kanto Electronics Application Development, and CPMA-V2 (program).
(3) Copper foil peeling strength The copper foil peeling strength was measured in accordance with JIS C 6481 and the adhesion to a conductor was measured.
(4) Solder heat resistance (moisture absorption heat resistance)
The solder heat resistance is determined by using a 50 mm square test piece obtained by etching the copper foils on both sides, and in a normal time and pressure cooker test (PCT) apparatus (conditions: 121 ° C., 2.2 atm) for a predetermined time (1 hour, The appearance of the test piece after immersion in the solder after being immersed in molten solder at 288 ° C. for 20 seconds was visually observed. In addition, the number in a table | surface means the number of sheets in which abnormality, such as generation | occurrence | production of a swelling and a measling, was not recognized among three test pieces after a solder immersion.
(5) Glass transition temperature (Tg) and coefficient of thermal expansion Glass transition temperature (Tg) and coefficient of thermal expansion (plate thickness direction, temperature range: 30 to 150 ° C.) are 5 mm square test pieces obtained by etching copper foils on both sides. In accordance with the IPC (The Institute for Interconnecting Electronic Circuits) standard using a thermomechanical measuring device (TMA) [Q400 (model number) manufactured by TA Instruments Japan Co., Ltd.] The transition temperature and the thermal expansion coefficient (linear expansion coefficient) were measured.
(6) Flame retardance 127 mm in length and 12 mm in width from the evaluation board from which the copper foil was removed by immersing the copper-clad laminate in a 10% by mass solution of ammonium persulfate (Mitsubishi Gas Chemical Co., Ltd.), which is a copper etching solution. A 7 mm test piece was cut out, and the flame retardancy was tested and evaluated according to the UL 94 test method (Method V) using the test piece.

  That is, flame contact for 10 seconds with a 20 mm flame was performed twice on the lower end of the test piece held vertically. Evaluation was performed in accordance with UL94 V method standards.

In addition, the symbol of each material in Table 4 and Table 5 is as follows.
(1) Curing accelerator (B)
<Organized oxide>
Perbutyl (registered trademark) I: t-butyl peroxyisopropyl monocarbonate, trade name (manufactured by NOF Corporation), 1 minute half-life temperature 158.8 ° C
Perhexa (registered trademark) HC: 1,1-di (t-hexylperoxy) cyclohexane, trade name (manufactured by NOF Corporation), 1 minute half-life temperature 149.2 ° C.
Perbutyl (registered trademark) P: α, α′-bis (t-butylperoxy) diisopropylbenzene, trade name (manufactured by NOF CORPORATION), 1 minute half-life temperature 175.4 ° C.
Parkmill (registered trademark) D: bis (1-phenyl-1-methylethyl) peroxide, trade name (manufactured by NOF Corporation), 1 minute half-life temperature 175.2 ° C.
Parkmill (registered trademark) P: diisopropylbenzene hydroperoxide, trade name (manufactured by NOF Corporation), 1 minute half-life temperature 232.5 ° C
<Imidazole-based curing agent>
G-8809L: Isocyanate mask imidazole (addition reaction product of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole), trade name (Daiichi Kogyo Seiyaku Co., Ltd.)
・ 2MZ-H: 2-methylimidazole, trade name (manufactured by Shikoku Kasei Co., Ltd.)
2E4MZ: 2-ethyl-4-methylimidazole, trade name (manufactured by Shikoku Kasei Co., Ltd.)
1B2MZ: 1-benzyl-2-methylimidazole, trade name (manufactured by Shikoku Kasei Co., Ltd.)
C11Z: 2-undecylimidazole, trade name (manufactured by Shikoku Kasei Co., Ltd.)
2MA-OK: 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct, trade name (manufactured by Shikoku Kasei Co., Ltd.)
<Phosphorus curing accelerator>
・ TPP-MK: Tetotaphenylphosphonium, trade name (made by Hokuko Sangyo Co., Ltd.)
・ TPP-S: Triphenylphosphonium, trade name (made by Hokuko Sangyo Co., Ltd.)
(2) Thermosetting resin (C)
NC-7000L: Naphthol novolac type epoxy resin, trade name (manufactured by Nippon Kayaku Co., Ltd.)
BMI-4000: 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane (manufactured by Daiwa Kasei Kogyo Co., Ltd.)
NC-3000H biphenyl aralkyl epoxy resin (Nippon Kayaku Co., Ltd.)
BA-230S: 2,2-bis (4-cyanatophenyl) propane prepolymer (solid content 75% by mass, manufactured by Lonza)
TAIC: triallyl isocyanurate (manufactured by Nippon Kasei Co., Ltd.)
(3) Inorganic filler (D)
SC2050-KNK: fused silica, trade name (manufactured by Admatechs)
AlOOH: Boehmite type aluminum hydroxide, density 3.0 g / cm ³ (manufactured by Kawai Lime Industry Co., Ltd.)
(4) Flame retardant (E)
OP-935: aluminum salt of dialkylphosphinic acid, metal salt of disubstituted phosphinic acid, phosphorus content: 23.5% by mass, trade name (manufactured by Clariant)
HCA-HQ: 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, cyclic organophosphorus compound, phosphorus content: 9.6% by mass Product name (Sanko Co., Ltd.)
(5) Polyphenylene ether / PPO640 (polyphenylene ether, number average molecular weight: about 16000, manufactured by SABIC Innovative Plastics)
(6) Compatibilizer / Tufprene A: Styrene-butadiene block copolymer (Asahi Kasei Chemicals Corporation)

  Examples 1 to 17 are resins containing at least one curing accelerator (B) selected from the group consisting of a polyphenylene ether derivative (A), an organic peroxide, an imidazole curing accelerator, and a phosphorus curing accelerator. It is an example using a composition. The laminates according to Examples 1 to 17 are superior in high-frequency characteristics than Comparative Examples 1 to 7 described later, and further balance good moisture absorption heat resistance, adhesion to conductors, glass transition temperature, thermal expansion characteristics and flame retardancy. Prepare well. Furthermore, when the peroxide and imidazole are used in combination (Examples 1 to 5), the moisture absorption heat resistance is superior.

Examples 18 to 22 are examples using a resin composition containing a polyphenylene ether derivative (A). As shown in Table 7, the dielectric loss tangent, CTE, and flame retardancy are superior to those of Comparative Examples 1 to 7 described later.

Comparative Examples 1 to 7 are examples using resin compositions not containing the polyphenylene ether derivative (A).

Furthermore, in order to evaluate the long-term stability of the varnish, the varnish prepared in Examples 1 to 5 was allowed to stand at room temperature for 1 week, and the presence or absence of subsequent gelation (leaving in the sample tube) was evaluated. The presence or absence of gelation was confirmed by the presence or absence of fluidity when the sample tube was gently inverted (upside down). The results are shown in Table 9.

As shown in Table 9, in the examples (Examples 3 to 5) using a peroxide having a 1 minute half-life temperature of 160 ° C. or higher, the varnish did not gel for more than one week, and in addition to the above-mentioned various properties, long-term stability It turns out that it is also excellent. It can also be understood that long-term stability is improved in the example using the mask imidazole (Example 9).

  The resin composition of the present invention has excellent high-frequency characteristics, high adhesion to a conductor, excellent heat resistance, low thermal expansion coefficient, flame retardancy, and high glass transition temperature. In addition, the resin composition of the present invention can keep raw material costs and substrate material manufacturing costs low, and prepregs and laminates provided using this resin composition are suitable for electronic component applications such as multilayer printed wiring boards. Can be used for

Claims (12)

  A resin composition comprising a polyphenylene ether derivative (A) having at least one N-substituted maleimide structure-containing group in the molecule. The resin composition according to claim 1, wherein the polyphenylene ether derivative (A) having at least one N-substituted maleimide structure-containing group in the molecule further has a structural unit represented by the following general formula (I). .

(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.) The resin composition according to claim 2, wherein the N-substituted maleimide structure-containing group is a group represented by the following general formula (Z).

(In the formula, each R ² independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. Y represents an integer of 0 to 4. A ¹ represents the following general formula (II), ( III), a group represented by (IV) or (V).)

(In the formula, each R ³ independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. P is an integer of 0 to 4.)

(In the formula, R ⁴ and R ⁵ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. A ² is an alkylene group having 1 to 5 carbon atoms and an alkylidene having 2 to 5 carbon atoms. A group, an ether group, a sulfide group, a sulfonyl group, a carbooxy group, a keto group, a single bond or a group represented by the following general formula (III-1): q and r are each independently an integer of 0 to 4. .)

(In the formula, R ⁶ and R ⁷ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. A ³ is an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, an ether group, A sulfide group, a sulfonyl group, a carboxyl group, a keto group, or a single bond, and s and t are each independently an integer of 0 to 4.)

(In the formula, n is an integer of 0 to 10.)

(In the formula, R ⁸ and R ⁹ 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.) ^{A 1} is the following formula in the formula (Z) (A-1) , (A-2), and a group represented by any one of (A-3), the resin composition according to claim 3 object.

The resin composition according to any one of claims 2 to 4, wherein the structural unit represented by the general formula (I) is a structural unit represented by the following formula (I ').

  The resin according to any one of claims 1 to 5, further comprising at least one curing accelerator (B) selected from the group consisting of an organic peroxide, an imidazole curing accelerator, and a phosphorus curing accelerator. Composition.   Furthermore, the resin composition of any one of Claims 1-6 containing the at least 1 sort (s) of thermosetting resin (C) chosen from an epoxy resin, cyanate ester resin, and a maleimide compound. The thermosetting resin (C) contains a maleimide compound (a) having at least two N-substituted maleimide structure-containing groups in the molecule or an aminobismaleimide compound (c) represented by the following general formula (VI). The resin composition according to claim 7.

(In the formula, A ⁴ is the same as the definition of A ^{1 in} the general formula (Z), and A ⁵ is a group represented by the following general formula (VII).)

^{(Wherein, R 17} and ^{R 18} each independently, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, .A ⁸ is an alkoxy group, a hydroxyl group or a halogen atom having 1 to 5 carbon atoms, 1 to carbon atoms 5 alkylene group, alkylidene group having 2 to 5 carbon atoms, ether group, sulfide group, sulfonyl group, carbooxy group, keto group, fluorenylene group, single bond, or the following general formula (VII-1) or (VII-2) Q ′ and r ′ are each independently an integer of 0 to 4.)

(In the formula, R ¹⁹ and R ²⁰ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. A ⁹ is an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, m- or a p-phenylenediisopropylidene group, an ether group, a sulfide group, a sulfonyl group, a carbooxy group, a keto group, or a single bond, and s ′ and t ′ are each independently an integer of 0 to 4.)

(Wherein R ²¹ is an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. A ¹⁰ and A ¹¹ are each independently an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, an ether group, A sulfide group, a sulfonyl group, a carbooxy group, a keto group, or a single bond, w is an integer of 0 to 4.)   A prepreg comprising the resin composition according to claim 1 and a sheet-like fiber reinforced base material.   The laminated board which has the hardened | cured material and metal foil of the resin composition of any one of Claims 1-8.   The multilayer printed wiring board which has the hardened | cured material of the resin composition of any one of Claims 1-8, or the laminated board of Claim 10.   The manufacturing method of a multilayer printed wiring board including the process of heat-press-molding the prepreg of Claim 9, or the laminated board of Claim 10.