JP2020033493A - Mixture of cyanate compound and curable composition - Google Patents

Abstract

To provide a novel mixture of a cyanate compound that gives a cured product having a high glass transition temperature, high thermal conductivity, and thermal decomposition resistance, and also has short varnish gel time, ensuring improved handleability, and a curable composition containing the mixture of the cyanate compound.SOLUTION: The present invention provides a mixture of a cyanate compound having two or more of predetermined repeating units, and/or two or more of predetermined groups.SELECTED DRAWING: None

Description

  The present invention relates to a mixture of a cyanate compound and a curable composition.

  In recent years, high integration and miniaturization of semiconductors widely used in electronic devices, communication devices, personal computers, and the like have been increasingly accelerated. Accordingly, various characteristics required for a laminate for a semiconductor package used for a printed wiring board have become increasingly severe. The required characteristics include, for example, characteristics such as low water absorption, moisture absorption heat resistance, flame retardancy, low dielectric constant, low dielectric loss tangent, heat resistance, chemical resistance, and high plating peel strength. However, to date, these required characteristics have not always been satisfied.

  Further, with the miniaturization and high density of the multilayer printed wiring board, the build-up layer used for the multilayer printed wiring board is multi-layered, and finer and higher density wiring is required. Since the multilayer printed wiring board suffers from the problem of expansion of warpage, a resin composition used as a material of the insulating layer is required to have higher properties such as a higher glass transition temperature.

  To solve these problems, Patent Literature 1 discloses an allyl group-containing resin composition having excellent bending strength and flexural modulus, having a low dielectric constant and a high glass transition temperature, and providing a cured product having excellent thermal conductivity. A resin composition containing a compound and a maleimide compound is disclosed.

  Further, Patent Document 2 discloses a resin composition capable of realizing a printed wiring board having a high glass transition temperature, excellent adhesion to metal and excellent thermal conductivity, and bis (3-allyl-4-). A resin composition containing a cyanate ester compound in which a hydroxyl group of (hydroxyphenyl) sulfone is cyanated and a maleimide compound is disclosed.

WO2017 / 006891 JP 2017-200966 A

  Patent Documents 1 and 2 both disclose that a high glass transition temperature and high thermal conductivity are achieved by using a cyanate compound having an allyl group. However, only using a cyanate compound having an allyl group tends to increase the water absorption of the obtained cured product, and it has been found that there is a concern that the gelling time of the composition may be reduced due to a long gel time. Was.

  The present invention has been made in view of the above problems, and can provide a cured product having a high glass transition temperature, high thermal conductivity, and high thermal decomposition resistance, and has a short varnish gel time and excellent solvent solubility. A mixture of a novel cyanate compound having excellent handleability by having a curable composition containing the mixture, and a cured product, a prepreg, and a metal foil-clad laminate using the curable composition It is an object of the present invention to provide a laminated resin sheet, a resin sheet, a printed wiring board, a sealing material, a fiber-reinforced composite material, and an adhesive.

  In order to solve the above-mentioned problems, the present inventors have made intensive studies. As a result, they have found that the above problem can be solved by using a mixture of a cyanate compound having a propenyl group and groups derived from different regioisomers, and completed the present invention. Was.

（式（１）〜（６）中、Ｘは、各々独立して、単結合、炭素数１〜５０の２価の有機基、窒素数１〜１０の２価の有機基、カルボニル基（−ＣＯ−）、カルボキシ基（−Ｃ（＝Ｏ）Ｏ−）、カルボニルジオキサイド基（−ＯＣ（＝Ｏ）Ｏ−）、スルホニル基（−ＳＯ₂−）、２価の硫黄原子（−Ｓ−）、及び２価の酸素原子（−Ｏ−）のいずれかを表し、Ｒ₁は、各々独立して、アルキル基、又はアリール基を表し、ａは、各々独立して、０以上の整数を表す。）

（式（７）〜（１０）中、Ｒ₁は、各々独立して、アルキル基、又はアリール基を表し、ａは、各々独立して、０以上の整数を表す。）
〔２〕
下記式（Ａ）で表される繰り返し単位及び／又は下記式（Ｂ）で表される基を有するシアン酸エステル化合物Ｉと、
下記式（Ａ）で表される繰り返し単位及び／又は下記式（Ｂ）で表される基を有するシアン酸エステル化合物ＩＩと、を含み、
前記シアン酸エステル化合物Ｉと前記シアン酸エステル化合物ＩＩは、下記式（Ａ）で表される繰り返し単位として異なる位置異性体単位及び／又は下記式（Ｂ）で表される基として異なる位置異性体基を有するという点において異なるものである、
〔１〕に記載のシアン酸エステル化合物の混合物。

（式（Ａ）中、Ｘは、各々独立して、単結合、炭素数１〜５０の２価の有機基、窒素数１〜１０の２価の有機基、カルボニル基（−ＣＯ−）、カルボキシ基（−Ｃ（＝Ｏ）Ｏ−）、カルボニルジオキサイド基（−ＯＣ（＝Ｏ）Ｏ−）、スルホニル基（−ＳＯ₂−）、２価の硫黄原子（−Ｓ−）、及び２価の酸素原子（−Ｏ−）のいずれかを表し、Ｒ₁は、各々独立して、アルキル基、又はアリール基を表し、ａは、各々独立して、０以上の整数を表す。）

（式（Ｂ）中、Ｒ₁は、各々独立して、アルキル基、又はアリール基を表し、ａは、各々独立して、０以上の整数を表す。）
〔３〕
プロペニル基当量が、１５０〜５，０００ｇ／ｅｑである、
〔１〕又は〔２〕に記載のシアン酸エステル化合物の混合物。
〔４〕
前記シアン酸エステル化合物が、下記式（１３）〜（１６）のいずれかで表される構造を有する化合物とその位置異性体である、
〔１〕〜〔３〕のいずれか一項に記載のシアン酸エステル化合物の混合物。

（式（１３）中、ｎは、平均繰り返し単位数を示し、２〜５０である。）

（式（１４）中、ｎは、平均繰り返し単位数を示し、２〜５０である。）

〔５〕
〔１〕〜〔４〕のいずれか一項に記載のシアン酸エステル化合物の混合物を含む、
硬化性組成物。
〔６〕
さらに、マレイミド化合物を含む、
〔５〕に記載の硬化性組成物。
〔７〕
さらに、〔１〕〜〔４〕のいずれか一項に記載の前記シアン酸エステル化合物の混合物に含まれるシアン酸エステル化合物以外のシアン酸エステル化合物、フェノール樹脂、エポキシ樹脂、オキセタン樹脂、ベンゾオキサジン化合物、及び重合可能な不飽和基を有する化合物からなる群より選択される少なくとも１種を含有する、
〔５〕又は〔６〕に記載の硬化性組成物。
〔８〕
前記硬化性組成物中の、マレイミド基量とマレイミド基を除く重合可能な不飽和基量の比率が、０．１：１〜１０：１である、
〔５〕〜〔７〕のいずれか１項に記載の硬化性組成物。
〔９〕
さらに、充填材を含有する、
〔５〕〜〔８〕のいずれか一項に記載の硬化性組成物。
〔１０〕
前記充填材の含有量が、樹脂固形分１００質量部に対して、５０〜１６００質量部である、
〔９〕に記載の硬化性組成物。
〔１１〕
〔５〕〜〔１０〕のいずれか一項に記載の硬化性組成物からなる、
硬化物。
〔１２〕
基材と、
前記基材に含浸又は塗布された、〔５〕〜〔１０〕のいずれか一項に記載の硬化性組成物と、を有する、
プリプレグ。
〔１３〕
少なくとも１枚以上積層した、〔１２〕に記載のプリプレグと、
前記プリプレグの片面又は両面に配置された金属箔と、を含む、
金属箔張積層板。
〔１４〕
支持体と、
前記支持体上に配された、〔５〕〜〔１０〕のいずれか一項に記載の硬化性組成物と、を含む、
樹脂シート。
〔１５〕
絶縁層と、
前記絶縁層の表面に形成された導体層と、を含み、
前記絶縁層が、〔５〕〜〔１０〕のいずれか一項に記載の硬化性組成物を含む、
プリント配線板。
〔１６〕
〔５〕〜〔１０〕のいずれか一項に記載の硬化性組成物を含む、
封止用材料。
〔１７〕
〔５〕〜〔１０〕のいずれか一項に記載の硬化性組成物と、強化繊維と、を含む、
繊維強化複合材料。
〔１８〕
〔５〕〜〔１０〕のいずれか一項に記載の硬化性組成物を含む、
接着剤。 That is, the present invention is as follows.
[1]
Having at least two of the repeating units represented by the following formulas (1) to (6) and / or at least two of the groups represented by the following formulas (7) to (10):
A mixture of cyanate compounds.

(In the formulas (1) to (6), X is each independently a single bond, a divalent organic group having 1 to 50 carbon atoms, a divalent organic group having 1 to 10 carbon atoms, a carbonyl group (- CO-), carboxyl group (-C (= O) O-) , carbonyl dioxide group (-OC (= O) O-) , a sulfonyl group (-SO ₂ -), _2-valent sulfur atom (-S- ) And a divalent oxygen atom (—O—), R ₁ each independently represents an alkyl group or an aryl group, and a each independently represents an integer of 0 or more. Represents.)

(In the formulas (7) to (10), R ₁ each independently represents an alkyl group or an aryl group, and a each independently represents an integer of 0 or more.)
[2]
A cyanate compound I having a repeating unit represented by the following formula (A) and / or a group represented by the following formula (B):
A repeating unit represented by the following formula (A) and / or a cyanate compound II having a group represented by the following formula (B):
The cyanate ester compound I and the cyanate ester compound II may be different positional isomer units as repeating units represented by the following formula (A) and / or different positional isomers as groups represented by the following formula (B) Is different in that it has a group,
A mixture of the cyanate compound according to [1].

(In the formula (A), X is each independently a single bond, a divalent organic group having 1 to 50 carbon atoms, a divalent organic group having 1 to 10 carbon atoms, a carbonyl group (-CO-), A carboxy group (—C (＝ O) O—), a carbonyldioxide group (—OC (＝ O) O—), a sulfonyl group (—SO ₂ —), a divalent sulfur atom (—S—), and 2 represents any value of the oxygen atom (-O-), R ₁ each independently represent an alkyl group, or an aryl group, a is each independently represents an integer of 0 or more.)

(In the formula (B), R ₁ each independently represents an alkyl group or an aryl group, and a each independently represents an integer of 0 or more.)
[3]
A propenyl group equivalent of 150 to 5,000 g / eq,
A mixture of the cyanate ester compound according to [1] or [2].
[4]
The cyanate compound is a compound having a structure represented by any of the following formulas (13) to (16) and a positional isomer thereof:
A mixture of the cyanate ester compound according to any one of [1] to [3].

(In the formula (13), n represents the average number of repeating units and is 2 to 50.)

(In the formula (14), n indicates the average number of repeating units, and is 2 to 50.)

[5]
Including a mixture of cyanate ester compounds according to any one of [1] to [4],
Curable composition.
[6]
Further, including a maleimide compound,
The curable composition according to [5].
[7]
Furthermore, a cyanate ester compound other than the cyanate ester compound contained in the mixture of the cyanate ester compounds according to any one of [1] to [4], a phenol resin, an epoxy resin, an oxetane resin, a benzoxazine compound And at least one selected from the group consisting of compounds having a polymerizable unsaturated group,
The curable composition according to [5] or [6].
[8]
In the curable composition, the ratio of the amount of the maleimide group and the amount of the polymerizable unsaturated group excluding the maleimide group is from 0.1: 1 to 10: 1.
The curable composition according to any one of [5] to [7].
[9]
Furthermore, containing a filler,
The curable composition according to any one of [5] to [8].
[10]
The content of the filler is 50 to 1600 parts by mass with respect to 100 parts by mass of the resin solid content.
The curable composition according to [9].
[11]
Consisting of the curable composition according to any one of [5] to [10],
Cured product.
[12]
A substrate,
Impregnated or coated on the substrate, and the curable composition according to any one of (5) to (10),
Prepreg.
[13]
At least one or more laminated, the prepreg according to [12],
And a metal foil disposed on one or both sides of the prepreg,
Metal foil clad laminate.
[14]
A support,
The curable composition according to any one of (5) to (10), which is disposed on the support,
Resin sheet.
[15]
An insulating layer,
And a conductor layer formed on the surface of the insulating layer,
The insulating layer contains the curable composition according to any one of [5] to [10],
Printed wiring board.
[16]
Including the curable composition according to any one of [5] to [10],
Sealing material.
[17]
[5] comprising the curable composition according to any one of [10] and a reinforcing fiber,
Fiber reinforced composite material.
[18]
Including the curable composition according to any one of [5] to [10],
adhesive.

  According to the present invention, it is possible to provide a cured product having a high glass transition temperature, high thermal conductivity, and high thermal decomposition resistance, and has excellent handling properties due to having a short varnish gel time and excellent solvent solubility. A novel cyanate compound, a curable composition containing the cyanate compound, and a cured product, a prepreg, a metal foil-clad laminate, a laminated resin sheet, a resin sheet, and a print using the curable composition. A wiring board, a sealing material, a fiber-reinforced composite material, and an adhesive can be provided.

  Hereinafter, an embodiment of the present invention (hereinafter, referred to as “the present embodiment”) will be described in detail, but the present invention is not limited thereto, and various modifications can be made without departing from the gist of the present invention. It is.

（式（１）〜（６）中、Ｘは、各々独立して、単結合、炭素数１〜５０の２価の有機基、窒素数１〜１０の２価の有機基、カルボニル基（−ＣＯ−）、カルボキシ基（−Ｃ（＝Ｏ）Ｏ−）、カルボニルジオキサイド基（−ＯＣ（＝Ｏ）Ｏ−）、スルホニル基（−ＳＯ₂−）、２価の硫黄原子（−Ｓ−）、及び２価の酸素原子（−Ｏ−）のいずれかを表し、Ｒ₁は、各々独立して、アルキル基、又はアリール基を表し、ａは、各々独立して、０以上の整数を表す。）

（式（７）〜（１０）中、Ｒ₁は、各々独立して、アルキル基、又はアリール基を表し、ａは、０以上の整数を表す。） (Mixture of cyanate compound)
The mixture of the cyanate ester compounds according to the present embodiment includes two or more of the repeating units that are different positional isomers represented by the following formulas (1) to (6) and / or the following formulas (7) to ( It has two or more of the groups that are different regioisomers represented by 10).

(In the formulas (1) to (6), X is each independently a single bond, a divalent organic group having 1 to 50 carbon atoms, a divalent organic group having 1 to 10 carbon atoms, a carbonyl group (- CO-), carboxyl group (-C (= O) O-) , carbonyl dioxide group (-OC (= O) O-) , a sulfonyl group (-SO ₂ -), _2-valent sulfur atom (-S- ) And a divalent oxygen atom (—O—), R ₁ each independently represents an alkyl group or an aryl group, and a each independently represents an integer of 0 or more. Represents.)

(In the formulas (7) to (10), R ₁ each independently represents an alkyl group or an aryl group, and a represents an integer of 0 or more.)

  Focusing on the relationship between the propenyl group bonded to the benzene ring and the group connected to another repeating unit, the formulas (1) and (3) are ortho-meta-substituted products, and the formula (2) is an ortho-meta-substituted product. -Para-substituted, formulas (4) and (5) are meta-para-substituted and formula (6) is meta-meta-substituted. Similarly, formulas (7) and (9) are meta-substituted products, formula (8) is a para-substituted product, and formula (10) is an ortho-substituted product. In addition, “two or more different regioisomeric units” or “two or more different regioisomeric groups” means different regioisomeric units as the repeating units represented by the above formulas (1) to (6), And / or two or more cyanate ester compounds having different positional isomer groups as groups represented by the following formulas (7) to (10).

  By using such a mixture, the crystallinity of the cyanate ester compound is reduced as compared with the cyanate ester compound which is not a mixture of isomers, so that the solvent solubility is further improved. In particular, the mixture of the cyanate ester compounds of the present embodiment is different only in the position isomer units or the position isomers of the position isomer groups. For example, two or more cyanates having the same X and other structures are the same. Those comprising an acid ester compound are preferred.

（式（Ａ）中、Ｘは、各々独立して、単結合、炭素数１〜５０の２価の有機基、窒素数１〜１０の２価の有機基、カルボニル基（−ＣＯ−）、カルボキシ基（−Ｃ（＝Ｏ）Ｏ−）、カルボニルジオキサイド基（−ＯＣ（＝Ｏ）Ｏ−）、スルホニル基（−ＳＯ₂−）、２価の硫黄原子（−Ｓ−）、及び２価の酸素原子（−Ｏ−）のいずれかを表し、Ｒ₁は、各々独立して、アルキル基、又はアリール基を表し、ａは、各々独立して、０以上の整数を表す。）

（式（Ｂ）中、Ｒ₁は、各々独立して、アルキル基、又はアリール基を表し、ａは、各々独立して、０以上の整数を表す。） In addition, the mixture of the cyanate compound of the present embodiment includes a cyanate compound I having a repeating unit represented by the following formula (A) and / or a group represented by the following formula (B), and a compound represented by the following formula ( A) a cyanate ester compound II having a repeating unit represented by A) and / or a group represented by the following formula (B), wherein the cyanate ester compound I and the cyanate ester compound II are represented by the following formula: It is preferable that they are different in that they have different positional isomer units as the repeating unit represented by (A) and / or different positional isomer groups as the group represented by the following formula (B). By using such a mixture, the crystallinity of the cyanate ester compound is reduced as compared with the cyanate ester compound which is not a mixture of isomers, so that the solvent solubility is further improved.

(In the formula (A), X is each independently a single bond, a divalent organic group having 1 to 50 carbon atoms, a divalent organic group having 1 to 10 carbon atoms, a carbonyl group (-CO-), A carboxy group (—C (＝ O) O—), a carbonyldioxide group (—OC (＝ O) O—), a sulfonyl group (—SO ₂ —), a divalent sulfur atom (—S—), and 2 represents any value of the oxygen atom (-O-), R ₁ each independently represent an alkyl group, or an aryl group, a is each independently represents an integer of 0 or more.)

(In the formula (B), R ₁ each independently represents an alkyl group or an aryl group, and a each independently represents an integer of 0 or more.)

（式（１７）中、Ａｒ₁は、各々独立して、ベンゼンテトライル基、ナフタレンテトライル基又はビフェニルテトライル基を示し、Ｒ₂は、各々独立して、水素原子、炭素数１〜６のアルキル基、炭素数６〜１２のアリール基、トリフルオロメチル基、又はフェノール性ヒドロキシ基を少なくとも１個有するアリール基を示し、Ｒ₃は、各々独立して、水素原子、炭素数１〜６のアルキル基、炭素数６〜１２のアリール基、炭素数１〜４のアルコキシル基、又はヒドロキシ基を示し、ｍは１〜５の整数を示す。）

（式（１８）中、Ａｒ₁は、各々独立して、ベンゼンテトライル基、ナフタレンテトライル基又はビフェニルテトライル基を示し、Ｒ₄は、各々独立して、水素原子、炭素数１〜６のアルキル基、炭素数６〜１２のアリール基、ベンジル基、炭素数１〜４のアルコキシル基、ヒドロキシ基、トリフルオロメチル基、又はシアナト基が少なくとも１個置換されたアリール基を示し、ｌは１〜５の整数を示す。） Specific examples of the divalent organic group having 1 to 50 carbon atoms in X in the above formulas include a methylene group, an ethylene group, a trimethylene group, a cyclopentylene group, a cyclohexylene group, a trimethylcyclohexylene group, and a biphenylylmethylene group. Dimethylmethylene-phenylene-dimethylmethylene group, fluorenediyl group, and phthalidodiyl group, and groups represented by the following formula (17) or (18). A hydrogen atom in the divalent organic group may be substituted with a halogen atom such as a fluorine atom and a chlorine atom, an alkoxyl group such as a methoxy group and a phenoxy group, a cyano group, and the like.

(In the formula (17), Ar ₁ each independently represents a benzenetetrayl group, a naphthalenetetrayl group or a biphenyltetrayl group, and R ₂ each independently represents a hydrogen atom, a carbon number of 1 to 6; Represents an alkyl group, an aryl group having 6 to 12 carbon atoms, a trifluoromethyl group, or an aryl group having at least one phenolic hydroxy group, and R ₃ is each independently a hydrogen atom, a carbon atom having 1 to 6 carbon atoms. Represents an alkyl group, an aryl group having 6 to 12 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, or a hydroxy group, and m represents an integer of 1 to 5.)

(In the formula (18), Ar ₁ each independently represents a benzenetetrayl group, a naphthalenetetrayl group or a biphenyltetrayl group, and R ₄ each independently represent a hydrogen atom, a carbon number of 1 to 6; Represents an aryl group having at least one substituted alkyl group, aryl group having 6 to 12 carbon atoms, benzyl group, alkoxyl group having 1 to 4 carbon atoms, hydroxy group, trifluoromethyl group, or cyanato group, and l is It represents an integer of 1 to 5.)

Furthermore, X in the formulas (1) to (6) also includes a divalent group represented by the following formula. Here, in the formula, z represents an integer of 4 to 7. Rk each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

  Examples of the divalent organic group having 1 to 10 nitrogen atoms in X in each of the above formulas include an imino group and a polyimide group.

  In each of the above formulas, the alkyl group is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, and 1-ethyl. A propyl group, a 2,2-dimethylpropyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, and a trifluoromethyl group.

  In each of the above formulas, the aryl group is not particularly limited. For example, a phenyl group, a xylyl group, a mesityl group, a naphthyl group, a phenoxyphenyl group, an ethylphenyl group, an o-, m- or p-fluorophenyl group, a dichlorophenyl Group, dicyanophenyl group, trifluorophenyl group, methoxyphenyl group, and o-, m- or p-tolyl group. Further, examples of the alkoxyl group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a tert-butoxy group.

  In each formula, a hydrogen atom in the alkyl group and the aryl group may be substituted with a halogen atom such as a fluorine atom or a chlorine atom, an alkoxyl group such as a methoxy group or a phenoxy group, or a cyano group.

  In each formula, a independently represents an integer of 0 or more, preferably 0 to 3, and more preferably 0 to 2.

（式（１１）中、ｎは、平均繰り返し単位数を示し、２〜５０である。）

The compound having a repeating unit represented by Formulas (1) to (6) or the compound having a group represented by Formulas (7) to (10) is not particularly limited. ) To (12), and more specifically, compounds represented by the following formulas (13) to (16). Use of such a compound tends to shorten the varnish gel time of the obtained curable composition, the balance between the glass transition temperature, the thermal conductivity and the thermal decomposition resistance of the obtained cured product, and improve the curability.

(In the formula (11), n represents the average number of repeating units and is 2 to 50.)

  The mixture of the cyanate compound of the present embodiment is a mixture of the multimer represented by the formula (11) and the dimer represented by the formula (12) when X is the same group. Is also good. In addition, in the multimer and the dimer having different n, there are different positional isomer units as the repeating unit represented by the formula (A) and / or different positional isomer groups as the group represented by the following formula (B). In this case, a mixture of different cyanate ester compounds is obtained. On the other hand, in the multimer and the dimer having different n, the repeating unit represented by the formula (A) and the group represented by the following formula (B) are the same, and the positional isomer unit or the positional isomer group is If not, they are considered to be one cyanate ester compound and not a mixture.

（式（１３）中、ｎは、平均繰り返し単位数を示し、２〜５０である。）

（式（１４）中、ｎは、平均繰り返し単位数を示し、２〜５０である。）

(In the formula (13), n represents the average number of repeating units and is 2 to 50.)

(In the formula (14), n indicates the average number of repeating units, and is 2 to 50.)

  In the above formulas (11) and (12), n is preferably 2 to 40, more preferably 3 to 20, and still more preferably 4 to 10. When n is 2 or more, the solvent solubility tends to be further improved.

  In addition, the mixture of the cyanate ester compound of the present embodiment is a cyanate ester compound represented by any of the cyanate ester compounds represented by the above formulas (11) to (16), and is represented by the formula (A) )) And / or two or more cyanate ester compounds having different regioisomeric groups as groups represented by the following formula (B) as repeating units represented by the following formula (B).

  A case where the repeating unit represented by the formula (A) or the group represented by the following formula (B) is the same except that the number n of the repeating units is different, and does not have a position isomer unit or a position isomer group. That is, in the compound which is the same cyanate ester compound in the present embodiment, the ratio of the multimer in which n is 2 or more to the dimer in which n is 1 is preferably 1 to 30% by mass, It is more preferably 3 to 20% by mass, and preferably 5 to 15% by mass. The use of such a cyanate compound tends to further improve the glass transition temperature, thermal conductivity, and thermal decomposition resistance of the obtained cured product.

  The mass average molecular weight of the cyanate compound of this embodiment is preferably from 150 to 10,000, more preferably from 150 to 7,000, and even more preferably from 150 to 5,000. When the molecular weight of the cyanate ester compound of the present embodiment is within the above range, the glass transition temperature of the obtained cured product, the thermal conductivity, the balance of thermal decomposition resistance, and the varnish gel time of the obtained curable composition is short. And the curability tends to be improved.

  When the cyanate compound of the present embodiment is a compound represented by any one of formulas (1) to (6), the molecular weight is preferably 150 to 10,000, more preferably 300 to 10,000, More preferably, it is 500 to 10,000. When the molecular weight of the cyanate ester compound of the present embodiment is within the above range, the glass transition temperature of the obtained cured product, the thermal conductivity, the balance of thermal decomposition resistance, and the varnish gel time of the obtained curable composition is short. And the curability tends to be improved.

  When the cyanate compound of the present embodiment is a compound represented by any one of formulas (7) to (10), the molecular weight is preferably from 150 to 1,000, more preferably from 150 to 500, and still more preferably. Is 150 to 400. When the molecular weight of the cyanate ester compound of the present embodiment is within the above range, the glass transition temperature of the obtained cured product, the thermal conductivity, the balance of thermal decomposition resistance, and the varnish gel time of the obtained curable composition is short. And the curability tends to be improved.

  The cyanato group equivalent of the cyanate ester compound of the present embodiment is preferably 150 to 5,000 g / eq, more preferably 150 to 2,000 g / eq, and still more preferably 150 to 600 g / eq. . When the cyanato group equivalent of the cyanate ester compound of the present embodiment is within the above range, the glass transition temperature of the obtained cured product, the thermal conductivity, the balance of thermal decomposition resistance, and the varnish of the obtained curable composition The gel time tends to be shorter and the curability tends to be improved.

  The propenyl group equivalent of the cyanate ester compound of this embodiment is preferably from 150 to 5,000 g / eq, more preferably from 150 to 2,000 g / eq, and still more preferably from 150 to 600 g / eq. When the unsaturated group equivalent of the cyanate compound of the present embodiment is within the above range, the glass transition temperature of the obtained cured product, the thermal conductivity, the balance of thermal decomposition resistance, and the varnish of the obtained curable composition The gel time tends to be shorter and the curability tends to be improved.

(Curable composition)
The curable composition of the present embodiment contains a mixture of the above-mentioned cyanate ester compounds, and if necessary, contains a maleimide compound, a filler, and other components.

(Cyanate compound)
The content of the mixture of the cyanate compound is preferably 3 to 80 parts by mass, more preferably 5 to 60 parts by mass, and still more preferably 5 to 50 parts by mass, based on 100 parts by mass of the resin solid content. Department. When the content of the cyanate ester compound of the present embodiment is within the above range, the glass transition temperature of the obtained cured product, the thermal conductivity, the balance of thermal decomposition resistance, and the varnish gel time of the obtained curable composition can be improved. Shortening tends to improve curability.

  In the present embodiment, the “resin solids” means, unless otherwise specified, the components of the curable composition excluding the solvent and the filler, and the “resin solids 100 parts by mass” It means that the total of the components excluding the solvent and the filler in the curable composition is 100 parts by mass.

(Maleimide compound)
The maleimide compound is not particularly limited as long as it is a compound having one or more maleimide groups in one molecule, and 4,4-diphenylmethanebismaleimide, phenylmethanemaleimide, m-phenylenebismaleimide, 2,2-bis (4- (4-maleimidophenoxy) -phenyl) propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6- Bismaleimide- (2,2,4-trimethyl) hexane, 4,4-diphenyletherbismaleimide, 4,4-diphenylsulfonebismaleimide, 1,3-bis (3-maleimidophenoxy) benzene, 1,3-bis ( 4-maleimidophenoxy) benzene, novolak-type maleimide compound, bife Ruararukiru maleimides and prepolymers of these maleimide compounds, or pre-polymer and the like of the maleimide compound and an amine compound. These maleimide compounds can be used alone or in combination of two or more.

  Among them, a novolak-type maleimide compound and a biphenylaralkyl-type bismaleimide compound are preferable. By using such a maleimide compound, heat resistance tends to be further improved.

  The maleimide group equivalent of the maleimide compound is preferably from 150 to 5,000 g / eq, more preferably from 150 to 2,000 g / eq, and still more preferably from 150 to 600 g / eq. When the maleimide group equivalent of the maleimide compound is within the above range, the glass transition temperature of the obtained cured product, the balance between thermal conductivity and thermal decomposition resistance, and the varnish gel time of the obtained curable composition is shortened and the curability is reduced. Tend to improve.

  The ratio of the amount of maleimide groups to the amount of polymerizable unsaturated groups excluding maleimide groups in the curable composition is preferably 0.1: 1 to 10: 1, and more preferably 0.1: 1 to 8: 1. : 1, more preferably 0.1: 1 to 7: 1. When the ratio of the amount of the maleimide group to the amount of the polymerizable unsaturated group excluding the maleimide group is within the above range, the glass transition temperature of the obtained cured product, the thermal conductivity, the balance of thermal decomposition resistance, and the obtained curability The varnish gel time of the composition tends to be short and the curability tends to be improved.

  The content of the maleimide compound is preferably from 10 to 70 parts by mass, more preferably from 30 to 65 parts by mass, and still more preferably from 40 to 60 parts by mass, based on 100 parts by mass of the resin solid content. When the content of the maleimide compound is within the above range, the glass transition temperature, thermal conductivity, and thermal decomposition resistance balance of the obtained cured product, and the varnish gel time of the obtained curable composition is shortened and the curability is improved. Tend to.

(Filler)
The curable composition of the present embodiment may further contain a filler. Although it does not specifically limit as a filler, For example, an inorganic filler and an organic filler are mentioned. As the filler, one type may be used alone, or two or more types may be used in combination.

  Examples of the inorganic filler include, but are not particularly limited to, natural silica, fused silica, synthetic silica, amorphous silica, aerosil, silica such as hollow silica; silicon compounds such as white carbon; titanium white, zinc oxide, magnesium oxide; Metal oxides such as zirconium oxide; nitrides such as boron nitride, aggregated boron nitride, silicon nitride, and aluminum nitride; metal sulfates such as barium sulfate; aluminum hydroxide, aluminum hydroxide heat-treated products (heat treatment of aluminum hydroxide) And a part of water of crystallization), boehmite, metal hydrates such as magnesium hydroxide; molybdenum compounds such as molybdenum oxide and zinc molybdate; zinc compounds such as zinc borate and zinc stannate; alumina; Clay, kaolin, talc, calcined clay, calcined chao Baked talc, mica, E glass, A glass, NE glass, C glass, L glass, D glass, S glass, M glass G20, short glass fiber (E glass, T glass, D glass, S glass, Q glass Etc.), hollow glass, spherical glass and the like.

  Examples of the organic filler include, but are not particularly limited to, rubber powders such as styrene-type powder, butadiene-type powder, and acrylic-type powder; core-shell-type rubber powder; silicone resin powder; silicone rubber powder; Can be

  The content of the filler is preferably 50 to 1600 parts by mass, more preferably 60 to 1200 parts by mass, and still more preferably 70 to 10000 parts by mass, based on 100 parts by mass of the resin solid content. Preferably it is 80 to 800 parts by mass. When the content of the filler is 50 parts by mass or more, the coefficient of thermal expansion tends to be further reduced.

(Silane coupling agent and wet dispersant)
The curable composition of the present embodiment may further include a silane coupling agent or a wetting and dispersing agent.

  The silane coupling agent is not particularly limited as long as it is a silane coupling agent generally used for surface treatment of an inorganic substance. For example, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ Aminosilane compounds such as -aminopropyltrimethoxysilane; epoxysilane compounds such as γ-glycidoxypropyltrimethoxysilane; acrylicsilane compounds such as γ-acryloxypropyltrimethoxysilane; N-β- (N- Cationic silane-based compounds such as vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride; and phenylsilane-based compounds. As the silane coupling agent, one type may be used alone, or two or more types may be used in combination.

  The wetting dispersant is not particularly limited as long as it is a dispersion stabilizer used for paints. For example, DISPER-110, 111, 118, 180, 161 and BYK-W996 manufactured by Big Chemie Japan KK , W9010 and W903.

[Other components]
The curable composition of the present embodiment may contain other components as necessary, in addition to the above components. The other components are not particularly limited, but include, for example, a cyanate compound other than the cyanate compound contained in the mixture of the above-described cyanate compound, a phenol resin, an epoxy resin, an oxetane resin, a benzoxazine compound, and polymerization. One or more compounds selected from the group consisting of compounds having a possible unsaturated group are exemplified.

(Other cyanate compounds)
The other cyanate ester compound is not particularly limited as long as it is a cyanate ester compound other than the cyanate ester compound contained in the mixture of the above-mentioned cyanate ester compounds, that is, a cyanate ester compound having at least a propenyl group.

（式（１９）中、Ｒ⁵は、各々独立に、水素原子又はメチル基を示し、ｎ₁は１以上の整数を表す。ｎ₁の上限値は、通常は１０であり、好ましくは６である。）

（式（２０）中、Ｒ⁶は、各々独立に、水素原子又はメチル基を示し、ｎ₂は１以上の整数を表す。ｎ₂の上限値は、通常は１０であり、好ましくは７である。） The cyanate compound is not particularly limited, and examples thereof include, for example, a naphthol aralkyl cyanate ester represented by the formula (19), a novolac cyanate ester represented by the formula (20), and a biphenylaralkyl cyanate ester , Bis (3,5-dimethyl-4-cyanatophenyl) methane, bis (4-cyanatophenyl) methane, 1,3-dicyanatobenzene, 1,4-dicyanatobenzene, 1,3,5-tricyanato Benzene, 1,3-dicyanatonaphthalene, 1,4-dicyanatonaphthalene, 1,6-dicyanatonaphthalene, 1,8-dicyanatonaphthalene, 2,6-dicyanatonaphthalene, 2,7-dicyanatonaphthalene, 1,3,6-tricyanatonaphthalene, 4,4′-dicyanatobiphenyl, bis (4-cyanatophene Nyl) ether, bis (4-cyanatophenyl) thioether, bis (4-cyanatophenyl) sulfone, and 2,2′-bis (4-cyanatophenyl) propane; prepolymers of these cyanate esters and the like. Can be The cyanate compound may be used alone or in combination of two or more.

(In the formula (19), R ⁵ each independently represents a hydrogen atom or a methyl group, and n ₁ represents an integer of 1 or more. The upper limit of n ₁ is usually 10, preferably 6. is there.)

(In the formula (20), R ⁶ each independently represents a hydrogen atom or a methyl group, and n ₂ represents an integer of 1 or more. The upper limit of n ₂ is usually 10, preferably 7 is there.)

  Among them, the cyanate compound is selected from the group consisting of a naphthol aralkyl cyanate ester represented by the formula (19), a novolak cyanate ester represented by the formula (20), and a biphenylaralkyl cyanate ester. It preferably contains at least one kind, more preferably at least one kind selected from the group consisting of a naphthol aralkyl cyanate ester represented by the formula (19) and a novolak type cyanate ester represented by the formula (20). . By using such a cyanate compound, a cured product having more excellent flame retardancy and higher curability tends to be obtained.

(Phenolic resin)
As the phenol resin, a generally known phenol resin having two or more hydroxy groups in one molecule can be used, and the type thereof is not particularly limited. Specific examples thereof include bisphenol A type phenol resin, bisphenol E type phenol resin, bisphenol F type phenol resin, bisphenol S type phenol resin, phenol novolak resin, bisphenol A novolak type phenol resin, glycidyl ester type phenol resin, aralkyl novolak type Phenol resin, biphenylaralkyl phenol resin, cresol novolak phenol resin, polyfunctional phenol resin, naphthol resin, naphthol novolak resin, polyfunctional naphthol resin, anthracene phenol resin, naphthalene skeleton modified novolak phenol resin, phenol aralkyl phenol resin , Naphthol aralkyl type phenolic resin, dicyclopentadiene type phenolic resin, biphenyl type Nord resins, alicyclic phenolic resins, polyol-type phenolic resin, a phosphorus-containing phenol resin, a hydroxyl group-containing silicone resins and the like, but is not particularly limited. These phenol resins can be used alone or in combination of two or more.

(Epoxy resin)
As the epoxy resin, a generally known epoxy resin can be used as long as it has two or more epoxy groups in one molecule, and the type thereof is not particularly limited. Specific examples thereof include bisphenol A epoxy resin, bisphenol E epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol A novolak epoxy resin, biphenyl epoxy resin, phenol novolak epoxy resin, and cresol novolak. Epoxy resin, xylene novolak epoxy resin, polyfunctional phenolic epoxy resin, naphthalene epoxy resin, naphthalene skeleton modified novolak epoxy resin, naphthylene ether epoxy resin, phenol aralkyl epoxy resin, anthracene epoxy resin, trifunctional Phenol type epoxy resin, 4-functional phenol type epoxy resin, triglycidyl isocyanurate, glycidyl ester type epoxy resin, alicyclic epoxy Fat, dicyclopentadiene novolak epoxy resin, biphenyl novolak epoxy resin, phenol aralkyl novolak epoxy resin, naphthol aralkyl novolak epoxy resin, aralkyl novolak epoxy resin, biphenyl aralkyl epoxy resin, naphthol aralkyl epoxy resin, dicyclo Pentadiene-type epoxy resin, polyol-type epoxy resin, phosphorus-containing epoxy resin, glycidylamine, compound in which double bond such as butadiene is epoxidized, compound obtained by reacting hydroxyl-containing silicone resin with epichlorohydrin, or a halide thereof And the like. These epoxy resins can be used alone or in combination of two or more.

  Among these, it is preferable that the epoxy resin is at least one selected from the group consisting of biphenylaralkyl type epoxy resin, naphthylene ether type epoxy resin, polyfunctional phenol type epoxy resin, and naphthalene type epoxy resin. By containing such an epoxy resin, the flame resistance and heat resistance of the obtained cured product tend to be further improved.

(Oxetane resin)
As the oxetane resin, generally known ones can be used, and the type thereof is not particularly limited. Specific examples thereof include alkyloxetanes such as oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, and 3,3-dimethyloxetane, 3-methyl-3-methoxymethyloxetane, and 3,3 ′ -Di (trifluoromethyl) perfluoxetane, 2-chloromethyloxetane, 3,3-bis (chloromethyl) oxetane, biphenyl-type oxetane, OXT-101 (trade name, manufactured by Toagosei), OXT-121 (tradename, manufactured by Toagosei) (Product name). These oxetane resins can be used alone or in combination of two or more.

(Benzoxazine compound)
As the benzoxazine compound, a generally known compound can be used as long as it has two or more dihydrobenzoxazine rings in one molecule, and the type thereof is not particularly limited. Specific examples thereof include bisphenol A-type benzoxazine BA-BXZ (trade name of Konishi Chemical) bisphenol F-type benzoxazine BF-BXZ (trade name of Konishi Chemical) and bisphenol S-type benzoxazine BS-BXZ (trade name of Konishi Chemical) Name). These benzoxazine compounds can be used alone or in combination of two or more.

(Compound having a polymerizable unsaturated group)
As the compound having a polymerizable unsaturated group other than the compound A, generally known compounds can be used, and the type thereof is not particularly limited. Specific examples thereof include vinyl compounds such as ethylene, propylene, styrene, divinylbenzene, and divinylbiphenyl; methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and polypropylene glycol di ( (Meth) of monohydric or polyhydric alcohol such as (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate Acrylates; epoxy (meth) acrylates such as bisphenol A type epoxy (meth) acrylate and bisphenol F type epoxy (meth) acrylate; allyl chloride, acetic acid ant , Allyl ether, propylene, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, diallyl isophthalate, allyl compounds such as diallyl maleate; include benzocyclobutene resin. These compounds having a polymerizable unsaturated group can be used alone or in combination of two or more.

(Curing accelerator)
The curable composition of the present embodiment may further include a curing accelerator. The curing accelerator is not particularly limited, but includes, for example, imidazoles such as triphenylimidazole; benzoyl peroxide, lauroyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, di-tert-butyl-di-perphthalate, and the like. Organic peroxides; azo compounds such as azobisnitrile; N, N-dimethylbenzylamine, N, N-dimethylaniline, N, N-dimethyltoluidine, 2-N-ethylanilinoethanol, tri-n-butylamine Tertiary amines such as pyridine, quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, tetramethylbutanediamine, N-methylpiperidine; phenols such as phenol, xylenol, cresol, resorcinol, catechol Organic metal salts such as lead naphthenate, lead stearate, zinc naphthenate, zinc octylate, tin oleate, dibutyltin malate, manganese naphthenate, cobalt naphthenate, and iron acetylacetone; these organic metal salts being phenol, bisphenol, etc. And inorganic metal salts such as tin chloride, zinc chloride and aluminum chloride; dioctyltin oxide; and other organic tin compounds such as alkyltin and alkyltin oxide. Among these, triphenylimidazole is particularly preferred because it promotes the curing reaction and tends to further improve the glass transition temperature.

〔solvent〕
The curable composition of the present embodiment may further include a solvent. By including the solvent, the viscosity at the time of preparing the curable composition is reduced, and the handleability is further improved, and the impregnating property to the base material described later tends to be further improved.

  The solvent is not particularly limited as long as it can dissolve a part or all of the resin component in the curable composition. For example, ketones such as acetone, methyl ethyl ketone and methyl cellosolve; toluene, xylene and the like Aromatic hydrocarbons; amides such as dimethylformamide; propylene glycol monomethyl ether and its acetate; One kind of the solvent may be used alone, or two or more kinds may be used in combination.

(Production method of curable composition)
The method for producing the curable composition of the present embodiment is not particularly limited, and includes, for example, a method in which the above-described components are sequentially mixed with a solvent and sufficiently stirred. At this time, known processes such as stirring, mixing, and kneading can be performed to uniformly dissolve or disperse the components. Specifically, the dispersibility of the filler in the curable composition can be improved by performing the stirring and dispersion treatment using a stirring tank provided with a stirrer having an appropriate stirring ability. The above-described stirring, mixing, and kneading treatments can be appropriately performed using, for example, a device for mixing such as a ball mill or a bead mill, or a known device such as a revolving or rotating type mixing device.

  Further, at the time of preparing the curable composition of the present embodiment, an organic solvent can be used as necessary. The type of the organic solvent is not particularly limited as long as the resin in the curable composition can be dissolved. The specific example is as described above.

[Application]
The curable composition of the present embodiment is preferably used as a cured product, a prepreg, a metal foil-clad laminate, a laminated resin sheet, a resin sheet, a printed wiring board, a sealing material, a fiber-reinforced composite material, or an adhesive. Can be. Hereinafter, these will be described.

(Cured product)
The cured product of the present embodiment is obtained by curing the curable composition. The method for producing the cured product is not particularly limited. For example, after the curable composition is melted or dissolved in a solvent, the composition is poured into a mold and cured by using heat or light under ordinary conditions. be able to. In the case of thermal curing, the curing temperature is not particularly limited, but is preferably in the range of 120 ° C. to 300 ° C. from the viewpoint that curing proceeds efficiently and deterioration of the obtained cured product is prevented. In the case of photo-curing, the wavelength range of light is not particularly limited, but it is preferable to cure the photocurable photopolymerization initiator or the like in a range of 100 nm to 500 nm in which curing proceeds efficiently.

[Prepreg]
The prepreg of this embodiment has a base material and the curable composition impregnated or applied to the base material. The method for producing the prepreg can be performed according to a conventional method, and is not particularly limited. For example, by impregnating or applying the resin component in the present embodiment to the base material, by heating in a drier at 100 to 200 ° C. for 1 to 30 minutes or the like, semi-curing (B-staging), The prepreg of the present embodiment can be manufactured.

  The content of the curable composition (including the filler) is preferably 30 to 90% by mass, more preferably 35 to 85% by mass, and still more preferably 40 to 80% by mass based on the total amount of the prepreg. % By mass. When the content of the curable composition is within the above range, moldability tends to be further improved.

  The substrate is not particularly limited, and a known substrate used for various printed wiring board materials can be appropriately selected and used depending on the intended use and performance. Specific examples of the fibers constituting the base material are not particularly limited. For example, glass fibers such as E glass, D glass, S glass, Q glass, spherical glass, NE glass, L glass, and T glass; Inorganic fibers other than glass; polyparaphenylene terephthalamide (Kevlar (registered trademark), manufactured by Dupont Co., Ltd.), copolyparaphenylene-3,4'oxydiphenylene terephthalamide (Technola (registered trademark), Teijin Techno Products ( Aromatic polyamides such as 2,6-hydroxynaphthoic acid / parahydroxybenzoic acid (Vectran (registered trademark), manufactured by Kuraray Co., Ltd.) and polyesters such as XXION (registered trademark, manufactured by KB Seiren); Polyparaphenylenebenzoxazole (Zylon (registered trademark), manufactured by Toyobo Co., Ltd.), polyimide Which organic fibers, and the like. Among these, at least one selected from the group consisting of E glass cloth, T glass cloth, S glass cloth, Q glass cloth, and organic fiber is preferable. These substrates may be used alone or in combination of two or more.

The shape of the substrate is not particularly limited, and examples thereof include woven fabric, nonwoven fabric, roving, chopped strand mat, and surfacing mat. The weaving method of the woven fabric is not particularly limited, but, for example, plain weaving, seaweed weaving, twill weaving, and the like are known, and can be appropriately selected and used depending on the intended use or performance from these known ones. . Further, those obtained by subjecting them to fiber opening treatment or glass woven fabrics surface-treated with a silane coupling agent or the like are preferably used. The thickness and mass of the substrate are not particularly limited, but usually those having a thickness of about 0.01 to 0.3 mm are suitably used. In particular, from the viewpoint of strength and water absorption, the substrate is preferably a glass woven fabric having a thickness of 200 μm or less and a mass of 250 g / m ² or less, and a glass woven fabric made of glass fibers of E glass, S glass, and T glass is preferable. More preferred.

[Laminated resin sheet]
The laminated resin sheet of the present embodiment has a support and the curable composition disposed on the support. The laminated resin sheet is used as one means of thinning, and for example, can be produced by directly applying and drying a curable composition on a support such as a metal foil or a film.

  The support is not particularly limited, but known supports used in various printed wiring board materials can be used. For example, polyimide film, polyamide film, polyester film, polyethylene terephthalate (PET) film, polybutylene terephthalate (PBT) film, polypropylene (PP) film, polyethylene (PE) film, polycarbonate film, ethylene tetrafluoroethylene copolymer film, and Organic film bases such as release films in which a release agent is applied to the surface of these films, conductive foils such as aluminum foil, copper foil and gold foil, plate-like inorganic materials such as glass plates, SUS plates and FPRs Films. Among them, an electrolytic copper foil and a PET film are preferable.

  Examples of the application method include a method in which a solution obtained by dissolving the curable composition of the present embodiment in a solvent is applied to a support using a bar coater, a die coater, a doctor blade, a baker applicator, or the like.

  It is preferable that the laminated resin sheet is obtained by applying the curable composition to a support and then semi-cured (B-staged). Specifically, for example, after the curable composition is applied to a support such as a copper foil, the composition is semi-cured by a method of heating for 1 to 60 minutes in a drier at 100 to 200 ° C. to obtain a laminated resin sheet. And the like. The amount of the curable composition adhered to the support is preferably in the range of 1 to 300 μm in the resin thickness of the laminated resin sheet.

[Single-layer resin sheet]
The single-layer resin sheet of the present embodiment contains a curable composition. The single-layer resin sheet is formed by molding the curable composition into a sheet. The method for producing the resin sheet can be performed according to a conventional method, and is not particularly limited. For example, the support can be obtained by peeling or etching the support from the laminated resin sheet. In addition, the solution obtained by dissolving the curable composition of the present embodiment in a solvent is supplied into a mold having a sheet-shaped cavity, and is then dried and formed into a sheet. And a single-layer resin sheet can be obtained.

(Metal foil clad laminate)
The metal foil-clad laminate of the present embodiment has at least one or more prepregs laminated, and metal foils disposed on one or both surfaces of the prepreg. That is, the metal foil-clad laminate of the present embodiment is obtained by laminating and curing the prepreg and the metal foil.

  The conductor layer can be a metal foil such as copper or aluminum. The metal foil used here is not particularly limited as long as it is used for a printed wiring board material, but a known copper foil such as a rolled copper foil or an electrolytic copper foil is preferable. Further, the thickness of the conductor layer is not particularly limited, but is preferably 1 to 70 μm, more preferably 1.5 to 35 μm.

The method for forming the metal foil-clad laminate and the molding conditions are not particularly limited, and the methods and conditions for general laminates for printed wiring boards and multilayer boards can be applied. For example, a multi-stage press machine, a multi-stage vacuum press machine, a continuous molding machine, an autoclave molding machine, or the like can be used when molding a metal foil-clad laminate. In the formation of the metal foil-clad laminate, the temperature is generally 100 to 350 ° C., the pressure is generally ^{2 to} 100 kgf / cm ² , and the heating time is generally 0.05 to 5 hours. Further, if necessary, post-curing can be performed at a temperature of 150 to 350 ° C. Also, a multilayer board can be formed by combining and laminating the above-described prepreg and a separately prepared wiring board for an inner layer.

[Printed wiring board]
The printed wiring board of the present embodiment includes an insulating layer and a conductor layer formed on a surface of the insulating layer, and the insulating layer includes the curable composition. The above-mentioned metal foil clad laminate can be suitably used as a printed wiring board by forming a predetermined wiring pattern. The above metal foil-clad laminate has good moldability and chemical resistance, and can be particularly effectively used as a printed wiring board for a semiconductor package requiring such performance.

  Specifically, the printed wiring board of the present embodiment can be manufactured, for example, by the following method. First, the above-mentioned metal foil-clad laminate (copper-clad laminate or the like) is prepared. An etching process is performed on the surface of the metal foil-clad laminate to form an inner circuit, thereby producing an inner substrate. The inner layer circuit surface of the inner layer substrate is subjected to a surface treatment to increase the adhesive strength as required, then the required number of prepregs are stacked on the inner layer circuit surface, and a metal foil for an outer layer circuit is further laminated on the outer side. Then, it is heated and pressurized to be integrally molded. In this way, a multilayer laminate in which an insulating layer made of a cured product of the base material and the curable composition is formed between the inner layer circuit and the metal foil for the outer layer circuit is manufactured. Next, after performing a drilling process for through holes and via holes on the multilayer laminate, a desmear process is performed to remove smear that is a residue of a resin derived from the resin component contained in the cured product layer. . Then, on the wall surface of this hole, a plated metal film is formed to conduct the inner layer circuit and the outer layer circuit metal foil, and then the outer layer circuit metal foil is etched to form the outer layer circuit, and the printed wiring board is manufactured. Is done.

  The printed wiring board obtained in the above-mentioned production example has an insulating layer and a conductor layer formed on the surface of the insulating layer, and the insulating layer includes the curable composition of the present embodiment described above. That is, the above-mentioned prepreg (the base material and the above-mentioned curable composition attached thereto) and the curable composition layer of the metal foil-clad laminate (the layer composed of the above-mentioned curable composition) are cured by the above-mentioned curing. The insulating layer containing the conductive composition is formed.

  When the metal foil-clad laminate is not used, a printed circuit board may be manufactured by forming a conductor layer to be a circuit on the prepreg, the laminated resin sheet, or the curable composition. . At this time, an electroless plating technique can be used for forming the conductor layer.

  The printed wiring board of the present embodiment is particularly effective as a printed wiring board for a semiconductor package, since the above-mentioned insulating layer has excellent properties such as (plating peel strength), bending strength, dielectric constant, and thermal weight loss rate. Can be used.

(Sealing material)
The sealing material of the present embodiment includes the curable composition of the present embodiment. As a method for producing the sealing material, a generally known method can be appropriately applied, and is not particularly limited. For example, a sealing material can be manufactured by mixing the above-mentioned curable composition and various known additives or solvents generally used in sealing material applications using a known mixer. . In addition, the method of adding each component at the time of mixing can be appropriately applied to a generally known method, and is not particularly limited.

(Fiber reinforced composite material)
The fiber-reinforced composite material of the present embodiment includes the curable composition of the present embodiment and a reinforcing fiber. As the reinforcing fibers, generally known fibers can be used and are not particularly limited. Specific examples thereof include glass fibers such as E glass, D glass, L glass, S glass, T glass, Q glass, UN glass, NE glass and spherical glass, carbon fiber, aramid fiber, boron fiber, PBO fiber, Examples include strong polyethylene fibers, alumina fibers, and silicon carbide fibers. The form and arrangement of the reinforcing fibers are not particularly limited, and can be appropriately selected from a woven fabric, a nonwoven fabric, a mat, a knit, a braid, a unidirectional strand, a roving, a chopped and the like. In addition, as a form of the reinforcing fiber, a preform (a laminated fabric base fabric made of a reinforcing fiber, or a stitch-integrated stitch yarn, or a fibrous structure such as a three-dimensional woven fabric or a braided fabric) is applied. Can also.

  As a method for producing these fiber-reinforced composite materials, generally known methods can be appropriately applied and are not particularly limited. Specific examples thereof include a liquid composite molding method, a resin film infusion method, a filament winding method, a hand lay-up method, and a pultrusion method. Among these, the resin transfer molding method, which is one of the liquid composite molding methods, requires that materials other than preforms, such as metal plates, foam cores, and honeycomb cores, be set in a molding die in advance. Since it is possible to cope with various uses, it is preferably used when mass-producing a relatively complex composite material in a short time.

〔adhesive〕
The adhesive of the present embodiment includes the curable composition of the present embodiment. As a method for producing the adhesive, a generally known method can be appropriately applied, and is not particularly limited. For example, an adhesive can be produced by mixing the above-mentioned curable composition and various known additives or solvents generally used for adhesives using a known mixer. In addition, the method of adding each component at the time of mixing can be appropriately applied to a generally known method, and is not particularly limited.

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. The present invention is not limited at all by the following Examples.

[Synthesis Example 1: Synthesis of naphthol aralkyl cyanate compound (SNCN)]
300 g of 1-naphthol aralkyl resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) (1.28 mol in terms of OH group) and 194.6 g (1.92 mol) of triethylamine (1.5 mol per 1 mol of hydroxy group) were dissolved in 1800 g of dichloromethane. This was designated as solution 1.

  On the other hand, 125.9 g (2.05 mol) of cyanogen chloride (1.6 mol per 1 mol of hydroxy group), 293.8 g of dichloromethane, 194.5 g (1.92 mol) of 36% hydrochloric acid (1.5 mol per 1 mol of hydroxy group) ) And 1205.9 g of water were mixed to form solution 2. The solution 1 was poured into the solution 2 over 30 minutes while maintaining the solution temperature at −2 to −0.5 ° C. while stirring the solution 2. After the addition of the solution 1 was completed, the mixture was stirred at the same temperature for 30 minutes, and then a solution (solution 3) obtained by dissolving 65 g (0.64 mol) of triethylamine (0.5 mol per 1 mol of hydroxy group) in 65 g of dichloromethane was added for 10 minutes. The solution 2 was poured down. After the addition of the solution 3, the mixture was stirred at the same temperature for 30 minutes to complete the reaction.

  Thereafter, the reaction solution was allowed to stand, and an organic phase and an aqueous phase were separated. The obtained organic phase was washed five times with 1300 g of water. The electric conductivity of the wastewater in the fifth washing was 5 μS / cm, and it was confirmed that the ionic compounds that could be removed by the washing with water were sufficiently removed.

The organic phase after washing with water was concentrated under reduced pressure, and finally concentrated and dried at 90 ° C. for 1 hour to obtain 331 g of a naphthol aralkyl cyanate compound (SNCN) (orange viscous substance) represented by the following formula. Was. The weight average molecular weight Mw of the obtained SNCN was 600. Further, the IR spectrum of SNCN showed an absorption at 2250 cm ^-1 (cyanate ester group) and no absorption of a hydroxy group. The cyanate group equivalent is 256 g / eq. Met.

[Synthesis Example 2: Phenol novolak type cyanate compound having an allyl group (APG-1CN)]
Allyl group-containing phenol novolak resin 700 g ("APG1" manufactured by Gunei Chemical Industry Co., Ltd .; OH group equivalent 146 g / eq .; OH group equivalent 4.79 mol; weight average molecular weight Mw 295) and 485.2 g (4.79 mol; hydroxy) of triethylamine (1.0 mol per 1 mol of group) was dissolved in 2100 g of dichloromethane, and this was designated as solution 1.

  456.8 g of cyanogen chloride (7.43 mol; 1.55 mol per mol of hydroxy group), 1074 g of dichloromethane, 704.1 g of 36% hydrochloric acid (6.95 mol; 1.45 mol per mol of hydroxy group), 3520.4 g of water was poured into Solution 1 over 50 minutes while maintaining the liquid temperature at −2 to −0.5 ° C. with stirring. After the addition of the solution 1 was completed, the mixture was stirred at the same temperature for 30 minutes, and then a solution of 630.7 g of triethylamine (6.23 mol; 1.3 mol per 1 mol of hydroxy group) dissolved in 630.7 g of dichloromethane (solution) 2) was poured over 30 minutes. After the addition of the solution 2 was completed, the mixture was stirred at the same temperature for 30 minutes to complete the reaction.

  Thereafter, the reaction solution was allowed to stand, and an organic phase and an aqueous phase were separated. The obtained organic phase was washed with 2 L of 0.1 N hydrochloric acid and then with 2000 g of water seven times. The electric conductivity of the wastewater after the seventh washing was 20 μS / cm, and it was confirmed that the ionic compounds that could be removed by the washing with water were sufficiently removed.

The organic phase after washing with water was concentrated under reduced pressure, and finally concentrated and dried at 90 ° C. for 1 hour to obtain 803 g of a target cyanate ester compound APG1CN (pale yellow viscous substance). The weight average molecular weight Mw of the obtained cyanate ester compound APG1CN was 350, and the cyanato group equivalent was 173 g / eq. And an allyl group equivalent of 176.5 g / eq. Met. In addition, the IR spectrum of APG1CN showed an absorption at 2263 cm -1 (cyanate group) and no absorption of a hydroxy group.

[Synthesis Example 3: Phenol novolak type cyanate compound having a propenyl group (APG-2CN)]
45 g of a propenyl group-containing phenol novolak resin ("APG2" manufactured by Gunei Chemical Industry Co., Ltd .; 152 g / eq. Of OH group equivalent; 0.296 mol in terms of OH group) and 30.0 g of triethylamine (0.296 mol; based on 1 mol of hydroxy group) (1.0 mol) was dissolved in 180 g of dichloromethane.

  29.1 g of cyanogen chloride (0.473 mol; 1.60 mol per mol of hydroxy group), 83.3 g of dichloromethane, 45 g of 36% hydrochloric acid (0.444 mol; 1.50 mol per mol of hydroxy group), 225 g of water was poured into the solution 3 over 15 minutes while maintaining the liquid temperature at −2 to −0.5 ° C. with stirring. After the addition of the solution 3 was completed, the mixture was stirred at the same temperature for 30 minutes, and then a solution in which 30.0 g of triethylamine (0.296 mol; 1.0 mol per 1 mol of hydroxy group) was dissolved in 30.0 g of dichloromethane (solution 4) was poured over 15 minutes. After the addition of the solution 4 was completed, the mixture was stirred at the same temperature for 30 minutes to complete the reaction.

  Thereafter, the reaction solution was allowed to stand, and an organic phase and an aqueous phase were separated. The obtained organic phase was washed with 125 mL of 0.1 N hydrochloric acid and then with 125 g of water four times. The electric conductivity of the wastewater in the fourth washing was 20 μS / cm, and it was confirmed that the ionic compounds that could be removed by the washing with water were sufficiently removed.

The organic phase after washing with water was concentrated under reduced pressure, and finally concentrated and dried at 90 ° C. for 1 hour to obtain 50 g of a target cyanate ester compound APG2CN (pale yellow viscous substance). The cyanate group equivalent of the obtained cyanate ester compound APG2CN was 177 g / eq. And the propenyl group equivalent is 180.6 g / eq. Met. In addition, the IR spectrum of APG2CN showed an absorption at 2250 cm -1 (cyanate group) and no absorption of a hydroxy group. Further, as confirmed by NMR, 62.7% of the obtained cyanate ester compounds in which the CH2 group was located at the para-position with respect to the cyanato group, and those obtained when the CH2 group was located at the ortho-position with respect to the cyanato group. And a mixture of 37.3% of the cyanate ester compounds having different regioisomeric units.

[Synthesis Example 4: Biphenylaralkyl-type cyanate compound having a propenyl group (BPN-CN)]
40.0 g (OH group equivalent: 255 g / eq.) (OH group equivalent: 0.157 mol) (OH group equivalent: 0.157 mol) and triethylamine: 16.0 g (0.157 mol) having a propenyl group-containing biphenylaralkyl-type phenol resin (BPN01, manufactured by Gunei Chemical Industry Co., Ltd.) ) (1.00 mol per 1 mol of hydroxy group) was dissolved in 200.0 g of dichloromethane.

  15.4 g (0.251 mol) of cyanogen chloride (1.60 mol per mol of hydroxy group), 36.0 g of dichloromethane, 24.6 g (0.243 mol) of 36% by mass hydrochloric acid (1 mol per mol of hydroxy group) (5.55 mol), and 152.7 g of water was poured into the solution 5 over 12 minutes while maintaining the liquid temperature at −5.5 to + 0.7 ° C. with stirring. After the addition of the solution 5 was completed, the mixture was stirred at the same temperature for 5 minutes, and then a solution in which 19.2 g (0.188 mol) of triethylamine (1.20 mol per 1 mol of hydroxy group) was dissolved in 19.7 g of dichloromethane ( Solution 6) was poured in over 6 minutes. After the addition of the solution 6, the mixture was stirred at the same temperature for 30 minutes to complete the reaction.

  Thereafter, the reaction solution was allowed to stand, and an organic phase and an aqueous phase were separated. The obtained organic phase was washed with 150 g of 0.1N hydrochloric acid and then five times with 150 g of water. The electric conductivity of the wastewater after the fifth washing was 39 μS / cm, and it was confirmed that the ionic compounds that could be removed by the washing with water were sufficiently removed.

The organic phase after washing with water is concentrated under reduced pressure, and finally concentrated and dried at 90 ° C. for 1 hour to obtain a biphenylaralkyl cyanate compound having a propenyl group (BPN-CN) represented by the following formula. Was. The IR spectrum of the obtained BPN-CN showed an absorption at 2250 cm ^-1 (cyanate group) and no absorption of a hydroxy group. The cyanate group equivalent is 292 g / eq. And the propenyl group equivalent is 379.5 g / eq. Met. In addition, as confirmed by NMR, the obtained cyanate ester compound had 54.3% of the cyanate group in which the CH2 group was located at the para-position and the CH2 group was located in the ortho-position with respect to the cyanato group. And a mixture of cyanate ester compounds having different regioisomeric units in an amount of 45.7%.

[Synthesis Example 5: Synthesis of bis (propenyl-4-hydroxyphenyl) sulfone-type cyanate compound (DSBS-CN)]
Bis (propenyl-4-hydroxyphenyl) sulfone (DABS-H, Nippon Kayaku Co., Ltd.) 30.1 g (OH group equivalent 165.2 g / eq.) (0.182 mol in terms of OH group) and 23.2 g of triethylamine (0.227 mol) (1.25 mol per 1 mol of hydroxy group) was dissolved in 180.3 g of dichloromethane.

  17.9 g (0.292 mol) of cyanogen chloride (1.60 mol per mol of hydroxy group), 42.0 g of dichloromethane, 28.7 g (0.283 mol) of 36% by mass hydrochloric acid (1 mol per mol of hydroxy group) (5.55 mol) and 177.3 g of water were poured over 90 minutes while stirring at a liquid temperature of -5.5 to + 0.7 ° C. After the addition of the solution 7 was completed, the mixture was stirred at the same temperature for 5 minutes, and then a solution in which 23.5 g (0.230 mol) of triethylamine (1.26 mol per 1 mol of hydroxy group) was dissolved in 24.0 g of dichloromethane ( Solution 8) was poured in over 6 minutes. After the addition of the solution 8 was completed, the mixture was stirred at the same temperature for 30 minutes to complete the reaction.

  Thereafter, the reaction solution was allowed to stand, and an organic phase and an aqueous phase were separated. The obtained organic phase was washed with 100 g of 0.1N hydrochloric acid and then with 100 g of water four times. The electric conductivity of the wastewater in the fourth washing was 55 μS / cm, and it was confirmed that the ionic compounds that could be removed by the washing with water were sufficiently removed.

The organic phase after washing with water is concentrated under reduced pressure, and finally concentrated and dried at 90 ° C. for 1 hour to obtain a bis (propenyl-4-hydroxyphenyl) sulfone cyanate compound (DSBS- 30.0 g of CN) were obtained. The IR spectrum of the obtained DSBS-CN showed an absorption at 2257 cm ^-1 (cyanate group) and no absorption of a hydroxy group. The cyanate group equivalent was 190.2 g / eq. And a propenyl group equivalent of 190.2 g / eq. Met.

[Examples 1 and 2, Comparative Example 1: Solvent solubility]
10 g of the mixture of regioisomers obtained in Synthesis Examples 3 and 4 or the compound obtained in Synthesis Example 5 was added to 10 g of methyl ethyl ketone, and the solvent solubility after stirring at room temperature for 30 minutes was visually confirmed. . A compound or a mixture of regioisomers having no residual residue was evaluated as good, and a compound with residual residue was evaluated as poor. Table 1 shows the results.

[Example 3]
A varnish was obtained by mixing 50 parts by mass of APG-2CN and 50 parts by mass of a biphenylaralkyl-type maleimide compound (maleimide group equivalent: 275 g / eq., MIR-3000, manufactured by Nippon Kayaku Co., Ltd.) in methyl ethyl ketone. 0.5 parts by mass of 2,4,5-Triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.05 parts by mass of zinc octylate (manufactured by Nippon Chemical Industry Co., Ltd.) are mixed with the obtained varnish, and methyl ethyl ketone is distilled off. By removing, a mixed resin powder was obtained. The mixed resin powder was filled in a mold having a side of 100 mm and a thickness of 0.8 mm, and vacuum-pressed at a pressure of 40 kg / cm 2 at a temperature of 230 ° C. for 120 minutes to obtain a cured product having a side of 100 mm and a thickness of 0.8 mm. .

[Example 4]
A varnish was obtained by mixing 40 parts by mass of SNCN, 10 parts by mass of APG-2CN, and 50 parts by mass of a maleimide compound (MIR-3000) in methyl ethyl ketone. 0.5 parts by mass of 2,4,5-Triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.05 parts by mass of zinc octylate (manufactured by Nippon Chemical Industry Co., Ltd.) are mixed with the obtained varnish, and methyl ethyl ketone is distilled off. By removing, a mixed resin powder was obtained. Thereafter, a cured product was obtained in the same manner as in Example 3.

[Example 5]
A varnish was obtained by mixing 30 parts by mass of SNCN, 20 parts by mass of APG-2CN, and 50 parts by mass of a maleimide compound (MIR-3000) in methyl ethyl ketone. 0.5 parts by mass of 2,4,5-Triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.05 parts by mass of zinc octylate (manufactured by Nippon Chemical Industry Co., Ltd.) are mixed with the obtained varnish, and methyl ethyl ketone is distilled off. By removing, a mixed resin powder was obtained. Thereafter, a cured product was obtained in the same manner as in Example 3.

[Example 6]
A varnish was obtained by mixing 30 parts by mass of SNCN, 20 parts by mass of BPN-CN, and 50 parts by mass of a maleimide compound (MIR-3000) in methyl ethyl ketone. 0.5 parts by mass of 2,4,5-Triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.05 parts by mass of zinc octylate (manufactured by Nippon Chemical Industry Co., Ltd.) are mixed with the obtained varnish, and methyl ethyl ketone is distilled off. By removing, a mixed resin powder was obtained. Thereafter, a cured product was obtained in the same manner as in Example 3.

[Comparative Example 2]
A varnish was obtained by mixing 50 parts by mass of SNCN and 50 parts by mass of a maleimide compound (MIR-3000) with methyl ethyl ketone. 0.5 parts by mass of 2,4,5-Triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.10 parts by mass of zinc octylate (manufactured by Nippon Chemical Industry Co., Ltd.) were mixed with the obtained varnish, and methyl ethyl ketone was distilled off. By removing, a mixed resin powder was obtained. Thereafter, a cured product was obtained in the same manner as in Example 3.

[Comparative Example 3]
A varnish was obtained by mixing 50 parts by mass of APG-1CN and 50 parts by mass of a maleimide compound (MIR-3000) with methyl ethyl ketone. 0.5 parts by mass of 2,4,5-Triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.10 parts by mass of zinc octylate (manufactured by Nippon Chemical Industry Co., Ltd.) were mixed with the obtained varnish, and methyl ethyl ketone was distilled off. By removing, a mixed resin powder was obtained. Thereafter, a cured product was obtained in the same manner as in Example 3.

[Varnish gel time]
A gel time (second) at 170 ° C. was measured using, as a sample, a mixture of 0.5 part by mass of 2,4,5-Triphenylimidazole and 0.10 part by mass of zinc octylate in the varnish described above. Table 2 shows the results.

[Glass transition temperature (Tg)]
In accordance with JIS-K7244-3 (JIS C6481), using a dynamic viscoelasticity measuring device (model number “AR2000” manufactured by TA Instruments Japan Co., Ltd.), a starting temperature of 30 ° C. and an ending temperature of 400 ° C. The dynamic viscoelasticity of the cured product was measured under the conditions of a heating rate of 3 ° C./min and a measurement frequency of 1 Hz. The maximum value of the loss elastic modulus (E ″) obtained at that time was defined as the glass transition temperature.
A: Glass transition temperature is 335 ° C. or more B: Glass transition temperature is 325 ° C. or more and less than 335 ° C. C: Glass transition temperature is 315 ° C. or more and less than 325 ° C. D: Glass transition temperature is less than 315 ° C.

[5% thermal decomposition temperature]
The thermogravimetric analysis of the cured product was performed using a thermogravimetric device (product name “TGA5200”, manufactured by SII Nanotechnology Co., Ltd.) under a nitrogen atmosphere under the condition of a heating rate of 10 ° C./min. The temperature at which the mass reduction rate was 5% was determined as a 5% thermal decomposition temperature. Table 2 shows the results.
A: 5% pyrolysis temperature is 410 ° C or higher B: 5% pyrolysis temperature is 400 ° C or higher and lower than 410 ° C C: 5% pyrolysis temperature is 390 ° C or higher and lower than 400 ° C D: 5% pyrolysis temperature is lower than 390 ° C

〔Thermal conductivity〕
The density of the obtained cured product was measured, and the specific heat was measured with a DSC (manufactured by TA Instrument, model Q100), and the heat diffusivity was measured with a xenon flash analyzer (manufactured by Bruker, product name “LFA447Nanoflash”). It was measured. Then, the thermal conductivity in the thickness direction was calculated from the following equation. Table 2 shows the results.
Thermal conductivity (W / m · K) = density (kg / m ³ ) × specific heat (kJ / kg · K) × thermal diffusivity (m ² / S) × 1000
A: Thermal conductivity is 0.194 W / m · K or more B: Thermal conductivity is 0.185 W / m · K or more and less than 0.194 W / m · K C: Thermal conductivity is 0.176 W / m · K or more Less than 0.185 W / m · K D: Thermal conductivity less than 0.176 W / m · K

  The cyanate ester compound of the present invention can be used industrially as a cured product, prepreg, metal foil-clad laminate, laminated resin sheet, resin sheet, printed wiring board, sealing material, fiber-reinforced composite material, or adhesive material. The availability of

Claims (18)

Having at least two of the repeating units represented by the following formulas (1) to (6) and / or at least two of the groups represented by the following formulas (7) to (10):
A mixture of cyanate compounds.

(In the formulas (1) to (6), X is each independently a single bond, a divalent organic group having 1 to 50 carbon atoms, a divalent organic group having 1 to 10 carbon atoms, a carbonyl group (- CO-), carboxyl group (-C (= O) O-) , carbonyl dioxide group (-OC (= O) O-) , a sulfonyl group (-SO ₂ -), _2-valent sulfur atom (-S- ) And a divalent oxygen atom (—O—), R ₁ each independently represents an alkyl group or an aryl group, and a each independently represents an integer of 0 or more. Represents.)

(In the formulas (7) to (10), R ₁ each independently represents an alkyl group or an aryl group, and a each independently represents an integer of 0 or more.) A cyanate compound I having a repeating unit represented by the following formula (A) and / or a group represented by the following formula (B):
A repeating unit represented by the following formula (A) and / or a cyanate compound II having a group represented by the following formula (B):
The cyanate ester compound I and the cyanate ester compound II may be different positional isomer units as repeating units represented by the following formula (A) and / or different positional isomers as groups represented by the following formula (B) Is different in that it has a group,
A mixture of the cyanate compound according to claim 1.

(In the formula (A), X is each independently a single bond, a divalent organic group having 1 to 50 carbon atoms, a divalent organic group having 1 to 10 carbon atoms, a carbonyl group (-CO-), A carboxy group (—C (＝ O) O—), a carbonyldioxide group (—OC (＝ O) O—), a sulfonyl group (—SO ₂ —), a divalent sulfur atom (—S—), and 2 represents any value of the oxygen atom (-O-), R ₁ each independently represent an alkyl group, or an aryl group, a is each independently represents an integer of 0 or more.)

(In the formula (B), R ₁ each independently represents an alkyl group or an aryl group, and a each independently represents an integer of 0 or more.) A propenyl group equivalent of 150 to 5,000 g / eq,
A mixture of the cyanate ester compounds according to claim 1. The cyanate compound is a compound having a structure represented by any of the following formulas (13) to (16) and a positional isomer thereof:
A mixture of the cyanate compound according to claim 1.

(In the formula (13), n represents the average number of repeating units and is 2 to 50.)

(In the formula (14), n indicates the average number of repeating units, and is 2 to 50.)

A mixture of the cyanate compound according to any one of claims 1 to 4,
Curable composition. Further, including a maleimide compound,
The curable composition according to claim 5. Furthermore, a cyanate compound other than the cyanate compound contained in the mixture of the cyanate compound according to any one of claims 1 to 4, a phenol resin, an epoxy resin, an oxetane resin, a benzoxazine compound, and Containing at least one selected from the group consisting of compounds having a polymerizable unsaturated group,
The curable composition according to claim 5. In the curable composition, the ratio of the amount of the maleimide group and the amount of the polymerizable unsaturated group excluding the maleimide group is from 0.1: 1 to 10: 1.
The curable composition according to claim 5. Furthermore, containing a filler,
The curable composition according to claim 5. The content of the filler is 50 to 1600 parts by mass with respect to 100 parts by mass of the resin solid content.
The curable composition according to claim 9. It consists of the curable composition according to any one of claims 5 to 10,
Cured product. A substrate,
The curable composition according to any one of claims 5 to 10, impregnated or applied to the base material,
Prepreg. The prepreg according to claim 12, wherein at least one or more sheets are laminated,
And a metal foil disposed on one or both sides of the prepreg,
Metal foil clad laminate. A support,
The curable composition according to any one of claims 5 to 10, which is disposed on the support.
Resin sheet. An insulating layer,
And a conductor layer formed on the surface of the insulating layer,
The insulating layer comprises the curable composition according to any one of claims 5 to 10,
Printed wiring board. Including the curable composition according to any one of claims 5 to 10,
Sealing material. The curable composition according to any one of claims 5 to 10, and a reinforcing fiber,
Fiber reinforced composite material. Including the curable composition according to any one of claims 5 to 10,
adhesive.