JP2017200997A - Composition, cured product, and laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel composition excellent in toughness and heat resistance after curing, a cured product thereof, and a laminate.SOLUTION: The composition of the present invention contains a polymer having a structural unit represented by at least one of the following formulae (1-1), (1-2) and (1-3) and a curable compound. In the formulae, each Ris independently a halogen atom, a 1-20C monovalent hydrocarbon group, a 1-20C monovalent halogenated hydrocarbon group, a nitro group, a cyano group, a primary to tertiary amino group, or a salt of a primary to tertiary amino group; each n is independently an integer of 0-2; when n is 2, a plurality of Rs may be the same or different and may be bonded together in any combination to form a part of a ring structure.SELECTED DRAWING: None

Description

  The present invention relates to a composition, a cured product, and a laminate. More specifically, the present invention relates to a novel composition excellent in toughness and heat resistance after curing, a cured product thereof, and a laminate.

  Conventionally, epoxy compounds having excellent heat resistance and chemical resistance after curing are known as typical curable compounds, and are widely used in various fields. However, in a cured product obtained from a material system containing an epoxy compound, lack of toughness is a problem, and further improvement in heat resistance is also required. Various methods for solving such problems have been studied. However, if the toughness is improved, the heat resistance is lowered, and if the heat resistance is improved, the toughness is lowered. The fact is that the balance between heat resistance and heat resistance has not been achieved. In addition, vinyl compounds such as divinylbenzene and other curable compounds such as cyanate ester compounds have the same problems as epoxy compounds.

  In recent years, the working environment of electronic materials and structural materials has become severe, and in a material system containing a curable compound, a material that is tougher and has excellent heat resistance is desired. Therefore, in order to meet this demand, studies have been made on a polymer alloy using an epoxy compound. Specifically, for example, a material system using polyethersulfone (PES) or polyphenylene ether (PPE) and an epoxy compound has been reported (for example, Patent Documents 1 to 3, Non-Patent Documents 1 to 2). See).

Japanese Patent No. 5630182 Japanese Patent Laid-Open No. 5-65352 Japanese Patent Laid-Open No. 2002-249531

J. et al. Appl. Poly. Sci. 106, 1318-1331 (2007) Polymer, 47 (5), 328-329 (1998)

  However, compatibility between toughness and heat resistance in conventional compositions is not yet sufficient, and further improvement in toughness and further improvement in toughness and heat resistance are required. In addition, further improvement in chemical resistance of the cured product against solvents and the like used in various manufacturing processes is also desired.

  This invention is made | formed in view of the said situation, and makes it a subject to provide the novel composition excellent in the toughness and heat resistance after hardening, its hardened | cured material, and a laminated body. Furthermore, it is an object of the present invention to provide a novel composition excellent in the performance balance of toughness, heat resistance and chemical resistance after curing, a cured product thereof, and a laminate.

〔式（１−１）〜（１−３）中、Ｒ^１は、それぞれ独立して、ハロゲン原子、炭素数１〜２０の１価の炭化水素基、炭素数１〜２０の１価のハロゲン化炭化水素基、ニトロ基、シアノ基、１〜３級アミノ基、又は１〜３級アミノ基の塩である。ｎは、それぞれ独立して、０〜２の整数である。ｎが２の場合、複数のＲ^１は、同一であっても異なっていてもよく、任意の組み合わせで結合して環構造の一部を形成していてもよい。〕
［２］前記硬化性化合物は、エポキシ化合物、シアネートエステル化合物、ビニル化合物、シリコーン化合物、オキサジン化合物、マレイミド化合物、及びアリル化合物のうちの少なくとも１種である前記［１］に記載の組成物。
［３］硬化助剤を更に含有する前記［１］又は［２］に記載の組成物。
［４］前記［１］乃至［３］のいずれかに記載の組成物が硬化してなることを特徴とする硬化物。
［５］基板と、前記基板上に、前記［１］乃至［３］のいずれかに記載の組成物を用いて形成された硬化物層と、を備えることを特徴とする積層体。 The present invention is as follows.
[1] containing a polymer having a structural unit represented by at least one of the following formulas (1-1), (1-2) and (1-3), and a curable compound. Characteristic composition.

[In formulas (1-1) to (1-3), each R ¹ independently represents a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent halogen having 1 to 20 carbon atoms. Or a salt of a primary hydrocarbon group, a nitro group, a cyano group, a primary to tertiary amino group, or a primary to tertiary amino group. n is an integer of 0-2 each independently. When n is 2, the plurality of R ¹ may be the same or different, and may be bonded in any combination to form part of the ring structure. ]
[2] The composition according to [1], wherein the curable compound is at least one of an epoxy compound, a cyanate ester compound, a vinyl compound, a silicone compound, an oxazine compound, a maleimide compound, and an allyl compound.
[3] The composition according to [1] or [2], further including a curing aid.
[4] A cured product obtained by curing the composition according to any one of [1] to [3].
[5] A laminate comprising a substrate and a cured product layer formed on the substrate using the composition according to any one of [1] to [3].

  Here, the “hydrocarbon group” includes a chain hydrocarbon group and a cyclic hydrocarbon group unless otherwise specified. The “hydrocarbon group” may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. The “chain hydrocarbon group” refers to a hydrocarbon group that does not include a cyclic structure but includes only a chain structure, and includes both a linear hydrocarbon group and a branched hydrocarbon group. “Cyclic hydrocarbon group” refers to a hydrocarbon group containing a cyclic structure, and includes both alicyclic hydrocarbon groups and aromatic hydrocarbon groups. The term “alicyclic hydrocarbon group” refers to a hydrocarbon group that includes only an alicyclic structure as a cyclic structure and does not include an aromatic ring structure, and includes a monocyclic alicyclic hydrocarbon group and a polycyclic alicyclic carbonization. Includes both hydrogen groups. However, it is not necessary to be composed only of the alicyclic structure, and a part thereof may include a chain structure. The “aromatic hydrocarbon group” refers to a hydrocarbon group containing an aromatic ring structure as a cyclic structure, and includes both monocyclic aromatic hydrocarbon groups and polycyclic aromatic hydrocarbon groups. However, it is not necessary to be composed only of an aromatic ring structure, and a part thereof may include a chain structure or an alicyclic structure. The “number of ring members” means the number of atoms constituting the cyclic structure, and in the case of polycyclic, means the number of atoms constituting the polycyclic ring.

  Since the composition of this invention contains the specific polymer excellent in compatibility with a sclerosing | hardenable compound, it is excellent in the toughness after hardening and heat resistance. Furthermore, this composition can provide a cured product having both high toughness and high heat resistance, and a laminate comprising the cured product. Moreover, according to the composition of this invention, the laminated body provided with the hardened | cured material excellent in the performance balance of toughness, heat resistance, and chemical resistance, and its hardened | cured material layer can be obtained. In particular, a cured product that has both excellent toughness and excellent heat resistance and excellent chemical resistance, and a laminate including the cured product layer can be obtained.

Hereinafter, the composition, cured product and laminate of the present invention will be described in detail.
<Composition>
The composition of the present invention is a composition containing the polymer and a curable compound.

[Polymer]
(First structural unit)
The polymer in the present invention (hereinafter also referred to as “[A] polymer”) is a structure represented by at least one of the following formulas (1-1), (1-2), and (1-3). It is a polymer having a unit (hereinafter also referred to as “first structural unit”).

〔式（１−１）〜（１−３）中、Ｒ^１は、それぞれ独立して、ハロゲン原子、炭素数１〜２０の１価の炭化水素基、炭素数１〜２０の１価のハロゲン化炭化水素基、ニトロ基、シアノ基、１〜３級アミノ基、又は１〜３級アミノ基の塩である。ｎは、それぞれ独立して、０〜２の整数である。ｎが２の場合、複数のＲ^１は、同一であっても異なっていてもよく、任意の組み合わせで結合して環構造の一部を形成していてもよい。〕

[In formulas (1-1) to (1-3), each R ¹ independently represents a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent halogen having 1 to 20 carbon atoms. Or a salt of a primary hydrocarbon group, a nitro group, a cyano group, a primary to tertiary amino group, or a primary to tertiary amino group. n is an integer of 0-2 each independently. When n is 2, the plurality of R ¹ may be the same or different, and may be bonded in any combination to form part of the ring structure. ]

Examples of the halogen atom represented by R ¹ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ include a monovalent chain hydrocarbon group, a monovalent alicyclic hydrocarbon group, and a monovalent aromatic hydrocarbon group. Etc.

  Examples of the monovalent chain hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, a t-butyl group, Examples thereof include alkyl groups such as n-pentyl group; alkenyl groups such as ethenyl group, propenyl group, butenyl group and pentenyl group; alkynyl groups such as ethynyl group, propynyl group, butynyl group and pentynyl group.

  Examples of the monovalent alicyclic hydrocarbon group include monocyclic cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group; polycyclic cycloalkyl groups such as norbornyl group and adamantyl group; And monocyclic cycloalkenyl groups such as cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, and cyclohexenyl group; and polycyclic cycloalkenyl groups such as norbornenyl group.

  Examples of the monovalent aromatic hydrocarbon group include aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group, and anthryl group; aralkyl groups such as benzyl group, phenethyl group, phenylpropyl group, and naphthylmethyl group. Etc.

Examples of the monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ include, for example, hydrogen of a monovalent hydrocarbon group having 1 to 20 carbon atoms exemplified as the group represented by R ^1. Examples include a group in which part or all of the atoms are substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

The substituent in the secondary amino group and tertiary amino group represented by R ¹ is not particularly limited, and examples thereof include monovalent hydrocarbon groups having 1 to 20 carbon atoms exemplified as the group represented by R ¹ above. Is mentioned. The cation constituting the cation moiety in the salt of the ^primary to tertiary amino group represented by R ¹ is not particularly limited and may be a known cation such as Na ⁺ .

R ¹ includes a halogen atom, a monovalent hydrocarbon group having 1 to 6 carbon atoms, and 1 having 1 to 6 carbon atoms from the viewpoint of improving polymerization reactivity and solubility of the monomer that gives the first structural unit. A valent halogenated hydrocarbon group, a nitro group, a cyano group, a primary to tertiary amino group, or a salt of a primary to tertiary amino group, preferably a fluorine atom, a chlorine atom, a methyl group, a nitro group, a cyano group, t- A butyl group, a phenyl group, and an amino group are more preferable. From the same viewpoint, n is preferably 0 or 1, and more preferably 0.

  The position of the other bond to one bond of the first structural unit is not particularly limited, but the meta position is preferable from the viewpoint of improving the polymerization reactivity of the monomer that provides the first structural unit.

  As a 1st structural unit, the said formula (1-2) which has a pyrimidine skeleton from a viewpoint which improves the polymerization reactivity of the monomer which gives a 1st structural unit, and a viewpoint which improves the solubility to various organic solvents. The structural unit represented by these is preferable.

  Examples of the monomer that gives the first structural unit in the [A] polymer include 4,6-dichloropyrimidine, 4,6-dibromopyrimidine, 2,4-dichloropyrimidine, 2,5-dichloropyrimidine, 2,5-dibromopyrimidine, 5-bromo-2-chloropyrimidine, 5-bromo-2-fluoropyrimidine, 5-bromo-2-iodopyrimidine, 2-chloro-5-fluoropyrimidine, 2-chloro-5-iodo Pyrimidine, 2,4-dichloro-5-fluoropyrimidine, 2,4-dichloro-5-iodopyrimidine, 5-chloro-2,4,6-trifluoropyrimidine, 2,4,6-trichloropyrimidine, 4,5 , 6-trichloropyrimidine, 2,4,5-trichloropyrimidine, 2,4,5,6-tetrachloropyrimidine, 2-pheni -4,6-dichloropyrimidine, 2-methylthio-4,6-dichloropyrimidine, 2-methylsulfonyl-4,6-dichloropyrimidine, 5-methyl-4,6-dichloropyrimidine, 2-amino-4,6- Dichloropyrimidine, 5-amino-4,6-dichloropyrimidine, 2,5-diamino-4,6-dichloropyrimidine, 4-amino-2,6-dichloropyrimidine, 5-methoxy-4,6-dichloropyrimidine, 5 -Methoxy-2,4-dichloropyrimidine, 5-fluoro-2,4-dichloropyrimidine, 5-bromo-2,4-dichloropyrimidine, 5-iodo-2,4-dichloropyrimidine, 2-methyl-4,6 -Dichloropyrimidine, 5-methyl-4,6-dichloropyrimidine, 6-methyl-2,4-dichloropyrimidine, 5-methyl 2,4-dichloropyrimidine, 5-nitro-2,4-dichloropyrimidine, 4-amino-2-chloro-5-fluoropyrimidine, 2-methyl-5-amino-4,6-dichloropyrimidine, 5- Bromo-4-chloro-2-methylthiopyrimidine; 3,6-dichloropyridazine, 3,5-dichloropyridazine, 4-methyl-3,6-dichloropyridazine; 2,3-dichloropyrazine, 2,6-dichloropyrazine, Examples include 2,5-dibromopyrazine, 2,6-dibromopyrazine, 2-amino-3,5-dibromopyrazine, 5,6-dicyano-2,3-dichloropyrazine and the like. In addition, these monomers may be used individually by 1 type, and may use 2 or more types together.

  In addition, as long as the [A] polymer in this invention has a 1st structural unit, it does not specifically limit about another structure.

(Second structural unit)
In addition to the first structural unit, the [A] polymer may have a structural unit represented by the following formula (2) (hereinafter also referred to as “second structural unit”).

〔式（２）中、Ａ^１及びＡ^２は、それぞれ独立して、−Ｏ−、−Ｓ−、又は−Ｎ（Ｒ^２）−である。Ｒ^２は、水素原子、又は炭素数１〜２０の１価の炭化水素基である。Ｘは２価の有機基である。〕

[In formula (2), ^{A 1} and ^{A 2} are each independently, -O -, - S-, or -N ^{(R 2)} - a. R ² is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. X is a divalent organic group. ]

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R ² include 1 carbon group exemplified as the group represented by R ¹ in the above formulas (1-1) to (1-3). -20 monovalent hydrocarbon groups and the like. R ² is preferably a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms from the viewpoint of improving the polymerization reactivity of the monomer that gives the second structural unit. When both A ¹ and A ² are —N (R ² ) —, the two R ² may be the same or different.

  Examples of the divalent organic group represented by X in the formula (2) include a group represented by the following formula (2-1).

〔式（２−１）中、Ｒ^４及びＲ^５は、それぞれ独立して、ハロゲン原子、炭素数１〜２０の１価の炭化水素基、炭素数１〜２０の１価のハロゲン化炭化水素基、炭素数１〜２０のアルコキシ基、炭素数１〜２０のアルキルチオ基、ニトロ基、シアノ基、カルボキシ基、スルホン酸基、ホスホン酸基、リン酸基、ヒドロキシ基、１〜３級アミノ基、カルボキシ基の塩、スルホン酸基の塩、ホスホン酸基の塩、リン酸基の塩、ヒドロキシ基の塩、又は１〜３級アミノ基の塩である。ｃ及びｄは、それぞれ独立して、０〜２の整数である。ａ及びｂは、それぞれ独立して、０〜８の整数である。ａが２以上の場合、複数のＲ^４は、同一であっても異なっていてもよく、任意の組み合わせで結合して環構造の一部を形成してもよい。ｂが２以上の場合、複数のＲ^５は、同一であっても異なっていてもよく、任意の組み合わせで結合して環構造の一部を形成してもよい。Ｑ及びＺは、それぞれ独立して、単結合、−Ｏ−、−Ｓ−、又は、−Ｎ（Ｒ^１７）−である。Ｒ^１７は、水素原子、炭素数１〜２０の１価の炭化水素基、又は炭素数１〜２０の１価のハロゲン化炭化水素基である。Ｌは、単結合、又は２価の有機基である。ｙは、０〜５の整数である。ｙが２以上の場合、複数のＱ、Ｌ及びＺは、それぞれ、同一であっても異なっていてもよい。ｙが２以上且つａが１以上の場合、複数のＲ^４は、同一であっても異なっていてもよい。Ｒ^６及びＲ^７は、それぞれ独立して、単結合、メチレン基、又は炭素数２〜４のアルキレン基である。〕

[In Formula (2-1), R ⁴ and R ⁵ are each independently a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent halogenated hydrocarbon having 1 to 20 carbon atoms. Group, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, a nitro group, a cyano group, a carboxy group, a sulfonic acid group, a phosphonic acid group, a phosphoric acid group, a hydroxy group, and a primary to tertiary amino group. A salt of a carboxy group, a salt of a sulfonic acid group, a salt of a phosphonic acid group, a salt of a phosphoric acid group, a salt of a hydroxy group, or a salt of a primary to tertiary amino group. c and d are each independently an integer of 0 to 2; a and b are each independently an integer of 0 to 8. When a is 2 or more, the plurality of R ⁴ may be the same or different, and may be bonded in any combination to form part of the ring structure. When b is 2 or more, the plurality of R ⁵ may be the same or different, and may be combined in any combination to form a part of the ring structure. Q and Z are each independently a single bond, —O—, —S—, or —N (R ¹⁷ ) —. R ¹⁷ is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms. L is a single bond or a divalent organic group. y is an integer of 0-5. When y is 2 or more, the plurality of Q, L, and Z may be the same or different. When y is 2 or more and a is 1 or more, the plurality of R ⁴ may be the same or different. R ⁶ and R ⁷ are each independently a single bond, a methylene group, or an alkylene group having 2 to 4 carbon atoms. ]

Examples of the halogen atom represented by R ⁴ and R ⁵ include the same halogen atoms as those exemplified as the halogen atom represented by R ¹ in the above formulas (1-1) to (1-3). Can be mentioned.

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R ⁴ and R ⁵ include the groups represented by R ¹ in the above formulas (1-1) to (1-3). And monovalent hydrocarbon groups having 1 to 20 carbon atoms.

Examples of the monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms represented by R ⁴ and R ⁵ include a group represented by R ¹ in the above formulas (1-1) to (1-3). And a group in which part or all of the hydrogen atoms of the monovalent hydrocarbon group having 1 to 20 carbon atoms exemplified as above are substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

Examples of the alkoxy group having 1 to 20 carbon atoms represented by R ⁴ and R ⁵ include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, a 2-methylpropoxy group, 1 -Methylpropoxy group, t-butoxy group, n-pentyloxy group and the like.

Examples of the alkylthio group having 1 to 20 carbon atoms represented by R ⁴ and R ⁵ include a methylthio group, an ethylthio group, an n-propylthio group, an i-propylthio group, an n-butylthio group, a 2-methylpropylthio group, 1-methylpropylthio group, t-butylthio group, n-pentylthio group and the like can be mentioned.

The substituents in the secondary amino group and the tertiary amino group represented by R ⁴ and R ⁵ are not particularly limited. For example, the group represented by R ¹ in the above formulas (1-1) to (1-3) And monovalent hydrocarbon groups having 1 to 20 carbon atoms exemplified as above. In addition, the secondary amino group and tertiary amino group represented by R ⁴ and R ⁵ may constitute a terminal composed of any one of the above-mentioned secondary amino structure and tertiary amino structure.

A cation moiety in a salt of a carboxy group, a salt of a sulfonic acid group, a salt of a phosphonic acid group, a salt of a phosphoric acid group, a salt of a hydroxy group, and a salt of a primary to tertiary amino group represented by R ⁴ and R ⁵ The cation which comprises is not specifically limited, It can be set as well-known cations, such as Na ^<+> .

R ⁴ and R ⁵ are each a halogen atom, a monovalent hydrocarbon group having 1 to 3 carbon atoms, or 1 to 3 carbon atoms from the viewpoint of improving the polymerization reactivity of the monomer that gives the second structural unit. Monovalent halogenated hydrocarbon group, alkoxy group having 1 to 3 carbon atoms, alkylthio group having 1 to 3 carbon atoms, nitro group, cyano group, carboxy group, sulfonic acid group, phosphonic acid group, phosphoric acid group, hydroxy group Group, primary to tertiary amino group, carboxy group salt, sulfonic acid group salt, phosphonic acid group salt, phosphoric acid group salt, hydroxy group salt, or primary to tertiary amino group salt are preferred. Atom, chlorine atom, methyl group, ethyl group, fluoromethyl group, methoxy group, methylthio group, nitro group, cyano group, carboxy group, sulfonic acid group, phosphonic acid group, phosphoric acid group, hydroxy group, primary to tertiary amino acids Group, carboxy Salts, salts of sulfonic acid group, a salt of phosphonic acid group, salts of the phosphate group, a salt of hydroxy group, or a primary to tertiary salts of amino groups are more preferred. From the same viewpoint, each of a and b is preferably 0 to 8, more preferably 0 to 4, and particularly preferably 0 to 2. Further, from the same viewpoint, c and d are each preferably 0 to 2, and more preferably 0 or 1.

-N ^{(R 17)} represented by Q and Z - ^{R 17} in the hydrogen atom, a monovalent hydrocarbon group or a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms having 1 to 20 carbon atoms It is. Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R ¹⁷ include the above formulas (1-1) to (1
Such monovalent hydrocarbon group exemplified having 1 to 20 carbon atoms as the group represented by R ¹ are exemplified in -3). Examples of the monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms represented by R ¹⁷ are the groups represented by R ¹ in the above formulas (1-1) to (1-3). Examples include a group in which part or all of the hydrogen atoms of a monovalent hydrocarbon group having 1 to 20 carbon atoms are substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. R ¹⁷ is preferably a hydrogen atom, a monovalent hydrocarbon group having 1 to 3 carbon atoms, or a monovalent halogenated hydrocarbon group having 1 to 3 carbon atoms.

Examples of the divalent organic group represented by L include —O—, —S—, —C (O) —, —S (O) —, —S (O) ₂ —, —C (O). -NH-, -C (O) -O-, a methylene group, an alkylene group having 2 to 20 carbon atoms, a halogenated methylene group, a halogenated alkylene group having 2 to 20 carbon atoms, a divalent cardo structure and the like. .

  Examples of the alkylene group having 2 to 20 carbon atoms represented by L include an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, a sec-butylene group, a t-butylene group, a neopentylene group, 4- Examples include a methyl-pentane-2-diyl group and a nonane-1,9-diyl group.

  Examples of the halogenated methylene group represented by L include groups in which part or all of the hydrogen atoms of the methylene group are substituted with halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom.

  Examples of the halogenated alkylene group having 2 to 20 carbon atoms represented by L include, for example, a part or all of the hydrogen atoms of the alkylene group having 2 to 20 carbon atoms exemplified as the group represented by L as a fluorine atom or chlorine. And a group substituted with a halogen atom such as an atom, bromine atom or iodine atom.

  Examples of the divalent cardo structure represented by L include a divalent group derived from fluorene (that is, a group obtained by removing two hydrogen atoms in fluorene), and a divalent group derived from phenolphthalein (that is, phenol). A group excluding two hydrogen atoms in phthalein), a group represented by the following formula (L1), and the like. In the divalent group derived from fluorene and the divalent group derived from phenolphthalein, part or all of the hydrogen atoms are substituted with a monovalent chain hydrocarbon group having 1 to 20 carbon atoms. Furthermore, some or all of the hydrogen atoms including the substituent may be substituted with fluorine atoms.

〔式（Ｌ１）中、Ｒ^ｃは、環員数５〜３０の２価の脂環式炭化水素基である。〕

[In Formula (L1), R ^c represents a divalent alicyclic hydrocarbon group having 5 to 30 ring members. ]

Examples of the divalent alicyclic hydrocarbon group having 5 to 30 ring members represented by R ^c include a monocyclic alicyclic hydrocarbon group having 5 to 15 ring members and a monocyclic ring having 5 to 15 ring members. Fluorinated alicyclic hydrocarbon groups, polycyclic alicyclic hydrocarbon groups having 7 to 30 ring members, polycyclic fluorinated alicyclic hydrocarbon groups having 7 to 30 ring members, and the like.

Examples of the monocyclic alicyclic hydrocarbon group having 5 to 15 ring members include cyclopentane-1,1-diyl group, cyclohexane-1,1-diyl group, and 3,3,5-trimethylcyclohexane-1. , 1-diyl group, cyclopentene-3,3-diyl group, cyclohexene-3,
3-diyl group, cyclooctane-1,1-diyl group, cyclodecane-1,1-diyl group, cyclododecane-1,1-diyl group, and some or all of hydrogen atoms of these groups have 1 to And a group substituted with 20 monovalent chain hydrocarbon groups.

  Examples of the monocyclic fluorinated alicyclic hydrocarbon group having 5 to 15 ring members include, for example, part of the hydrogen atoms of the groups exemplified as the monocyclic alicyclic hydrocarbon group having 5 to 15 ring members or Examples thereof include groups that are all substituted with fluorine atoms.

Examples of the polycyclic alicyclic hydrocarbon group having 7 to 30 ring members include norbornane, norbornene, adamantane, tricyclo [5.2.1.0 ^2,6 ] decane, and tricyclo [5.2.1. Polycyclic fats such as 0 ^2,6 ] heptane, pinane, camphane, decalin, nortricyclane, perhydroanthracene, perhydroazulene, cyclopentanohydrophenanthrene, bicyclo [2.2.2] -2-octene A group excluding two hydrogen atoms bonded to one carbon atom of a cyclic hydrocarbon, a part or all of the hydrogen atoms of these groups is a monovalent chain hydrocarbon group having 1 to 20 carbon atoms; Examples include substituted groups.

  Examples of the polycyclic fluorinated alicyclic hydrocarbon group having 7 to 30 ring members include, for example, part of the hydrogen atoms of the groups exemplified as the polycyclic alicyclic hydrocarbon group having 7 to 30 ring members or Examples thereof include groups that are all substituted with fluorine atoms.

L is a single bond, —O—, —S—, —C (O) —, —S (O) —, —S (O) ₂ —, from the viewpoint of the structural stability of the polymer [A]. -C (O) -NH-, -C (O) -O-, methylene group, alkylene group having 2 to 5 carbon atoms, halogenated methylene group, halogenated alkylene group having 2 to 10 carbon atoms, or divalent A cardo structure is preferred. From the same viewpoint, y is preferably 0 to 4, more preferably 0 to 3.

Examples of the alkylene group having 2 to 4 carbon atoms represented by R ⁶ and R ⁷ include an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, a sec-butylene group, and a t-butylene group. Can be mentioned. R ⁶ and R ⁷ are each preferably a single bond, a methylene group, or an ethylene group from the viewpoint of improving the polymerization reactivity of the monomer that gives the second structural unit.

  Further, examples of the divalent organic group represented by X in the formula (2) include groups represented by the following formula (2-2).

〔式（２−２）中、Ｒ^ａ及びＲ^ｂは、それぞれ独立して、環員数５〜３０の２価の脂環式炭化水素骨格である。Ｒ^８及びＲ^９は、それぞれ独立して、ハロゲン原子、炭素数１〜２０の１価の炭化水素基、炭素数１〜２０の１価のハロゲン化炭化水素基、炭素数１〜２０のアルコキシ基、炭素数１〜２０のアルキルチオ基、ニトロ基、シアノ基、カルボキシ基、スルホン酸基、ホスホン酸基、リン酸基、ヒドロキシ基、１〜３級アミノ基、カルボキシ基の塩、スルホン酸基の塩、ホスホン酸基の塩、リン酸基の塩、ヒドロキシ基の塩、又は１〜３級アミノ基の塩である。ｅ及びｆは、それぞれ独立して、０〜２０の整数である。ｅが２以上の場合、複数のＲ^８は、同一であっても異なっていてもよく、任意の組み
合わせで結合して環構造の一部を形成してもよい。ｆが２以上の場合、複数のＲ^９は、同一であっても異なっていてもよく、任意の組み合わせで結合して環構造の一部を形成してもよい。Ｑ及びＺは、それぞれ独立して、単結合、−Ｏ−、−Ｓ−、又は、−Ｎ（Ｒ^１８）−である。Ｒ^１８は、水素原子、炭素数１〜２０の１価の炭化水素基、又は炭素数１〜２０の１価のハロゲン化炭化水素基である。Ｌは、単結合、又は２価の有機基である。ｙは、０〜５の整数である。ｙが２以上の場合、複数のＱ、Ｌ及びＺは、それぞれ、同一であっても異なっていてもよい。ｙが２以上且つｅが１以上の場合、複数のＲ^８は、同一であっても異なっていてもよい。Ｒ^１０及びＲ^１１は、それぞれ独立して、単結合、メチレン基、又は炭素数２〜４のアルキレン基である。〕

[In Formula (2-2), R ^a and R ^b are each independently a divalent alicyclic hydrocarbon skeleton having 5 to 30 ring members. R ⁸ and R ⁹ are each independently a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, or an alkoxy having 1 to 20 carbon atoms. Group, alkylthio group having 1 to 20 carbon atoms, nitro group, cyano group, carboxy group, sulfonic acid group, phosphonic acid group, phosphoric acid group, hydroxy group, primary to tertiary amino group, salt of carboxy group, sulfonic acid group Salt, phosphonic acid group salt, phosphoric acid group salt, hydroxy group salt, or primary to tertiary amino group salt. e and f are each independently an integer of 0 to 20. When e is 2 or more, the plurality of R ⁸ may be the same or different and may be combined in any combination to form a part of the ring structure. When f is 2 or more, the plurality of R ⁹ may be the same or different, and may be combined in any combination to form a part of the ring structure. Q and Z are each independently a single bond, —O—, —S—, or —N (R ¹⁸ ) —. R ¹⁸ is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms. L is a single bond or a divalent organic group. y is an integer of 0-5. When y is 2 or more, the plurality of Q, L, and Z may be the same or different. When y is 2 or more and e is 1 or more, the plurality of R ⁸ may be the same or different. R ¹⁰ and R ¹¹ are each independently a single bond, a methylene group, or an alkylene group having 2 to 4 carbon atoms. ]

Examples of the divalent alicyclic hydrocarbon skeleton having 5 to 30 ring members represented by R ^a and R ^b include, for example, a monocyclic alicyclic hydrocarbon skeleton having 5 to 15 ring members and 7 to 30 ring members. And a polycyclic alicyclic hydrocarbon skeleton. In addition, the position of the other bond to one bond in the divalent alicyclic hydrocarbon skeleton having 5 to 30 ring members represented by R ^a and R ^b is not particularly limited.

  Examples of the monocyclic alicyclic hydrocarbon skeleton having 5 to 15 ring members include, for example, cyclopentane-diyl group, cyclohexane-diyl group, cyclopentene-diyl group, cyclohexene-diyl group, cyclooctane-diyl group, cyclodecane- A diyl group, a cyclododecane-diyl group, etc. are mentioned.

Examples of the polycyclic alicyclic hydrocarbon skeleton having 7 to 30 ring members include norbornane, norbornene, adamantane, tricyclo [5.2.1.0 ^2,6 ] decane, and tricyclo [5.2.1. Polycyclic fats such as 0 ^2,6 ] heptane, pinane, camphane, decalin, nortricyclane, perhydroanthracene, perhydroazulene, cyclopentanohydrophenanthrene, bicyclo [2.2.2] -2-octene Examples include a group in which two hydrogen atoms are removed from a cyclic hydrocarbon.

The divalent alicyclic hydrocarbon skeleton having 5 to 30 ring members represented by R ^a and R ^b is respectively cyclopentane-diyl group, cyclohexane-diyl group, norbornene from the viewpoint of maintaining high heat resistance. A group in which two hydrogen atoms are removed, or a group in which part or all of the hydrogen atoms in these groups are substituted with R ⁸ or R ⁹ is preferred.

For R ⁸ and R ⁹ in Formula (2-2), all the descriptions regarding R ⁴ in Formula (2-1) can be applied as they are. e and f are preferably 0 to 10 and more preferably 0 to 5 from the viewpoint of improving the polymerization reactivity of the monomer giving the second structural unit.

For Q, Z, R ¹⁸ , L, and y in Formula (2-2), all the descriptions regarding Q, Z, R ¹⁷ , L, and y in Formula (2-1) can be applied as they are. it can.

For R ¹⁰ and R ¹¹ in Formula (2-2), all the descriptions regarding R ⁶ in Formula (2-1) can be applied as they are.

  Further, examples of the divalent organic group represented by X in the formula (2) include groups represented by the following formula (2-3).

〔式（２−３）中、Ｒ^１２は、水素原子、炭素数１〜２０の１価の炭化水素基、又は炭素数１〜２０の１価のハロゲン化炭化水素基である。Ｒ^１３及びＲ^１４は、それぞれ独立して、炭素数１〜２０の２価の鎖状又は脂環式の炭化水素基、又は炭素数１〜２０の２価の鎖状又は脂環式のハロゲン化炭化水素基である。ｇは、０又は１である。ｈは、１〜１０の整数である。ｈが２以上の場合、複数のＲ^１２及びＲ^１４は、それぞれ、同一であっても異なっていてもよい。〕

[In formula (2-3), R ¹² represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms. R ¹³ and R ¹⁴ are each independently a divalent chain or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a divalent chain or alicyclic halogen group having 1 to 20 carbon atoms. Hydrocarbon group. g is 0 or 1. h is an integer of 1-10. When h is 2 or more, the plurality of R ¹² and R ¹⁴ may be the same or different. ]

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R ¹² include the carbon number exemplified as the group represented by R ¹ in the above formulas (1-1) to (1-3). Examples thereof include 1-20 monovalent hydrocarbon groups.

Examples of the monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms represented by R ¹² include the groups represented by R ¹ in the above formulas (1-1) to (1-3). Examples include a group in which part or all of the hydrogen atoms of a monovalent hydrocarbon group having 1 to 20 carbon atoms are substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

R ¹² is a hydrogen atom, a monovalent hydrocarbon group having 1 to 3 carbon atoms, or a monovalent hydrocarbon group having 1 to 3 carbon atoms from the viewpoint of improving the polymerization reactivity of the monomer that gives the second structural unit. Halogenated hydrocarbon groups are preferred.

Examples of the divalent chain hydrocarbon group having 1 to 20 carbon atoms represented by R ¹³ and R ¹⁴ include methylene group, ethylene group, 1,2-propylene group, 1,3-propylene group, tetra Methylene group, pentamethylene group, hexamethylene group, 1-methyl-1,3-propylene group, 2-methyl-1,3-propylene group, 2-methyl-1,2-propylene group, 1-methyl-1, Examples thereof include linear or branched alkylene groups such as 4-butylene group and 2-methyl-1,4-butylene group.

Examples of the divalent alicyclic hydrocarbon group (carbon number: 3 to 20) represented by R ¹³ and R ¹⁴ include cyclobutylene groups such as cyclopropylene group and 1,3-cyclobutylene group, 1 Monocyclic hydrocarbon groups such as cyclopentylene groups such as 1,3-cyclopentylene groups, cyclohexylene groups such as 1,4-cyclohexylene groups; 1,4-norbornylene groups, 2,5-norbornylene groups, etc. And polycyclic hydrocarbon groups such as an adamantylene group such as a norbornylene group, a 1,5-adamantylene group, and a 2,6-adamantylene group.

Examples of the divalent chain or alicyclic halogenated hydrocarbon group having 1 to 20 carbon atoms represented by R ¹³ and R ¹⁴ include, for example, the carbons exemplified as the groups represented by R ¹³ and R ¹⁴ above. Examples include a group in which part or all of the hydrogen atoms in the divalent chain or alicyclic hydrocarbon group of 1 to 20 are substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. .

R ¹³ and R ¹⁴ are each a divalent chain hydrocarbon group having 1 to 3 carbon atoms or 4 to 10 carbon atoms from the viewpoint of improving the polymerization reactivity of the monomer that gives the second structural unit. A divalent alicyclic hydrocarbon group, a divalent chain halogenated hydrocarbon group having 1 to 3 carbon atoms, or a divalent alicyclic halogenated hydrocarbon group having 4 to 10 carbon atoms. preferable. From the same viewpoint, h is preferably 0 to 5, more preferably 0 to 3.

  Further, examples of the divalent organic group represented by X in the formula (2) include groups represented by the following formula (2-4).

〔式（２−４）中、Ｒ^１５及びＲ^１６は、それぞれ独立して、炭素数１〜２０の２価の鎖状又は脂環式の炭化水素基、又は炭素数１〜２０の２価の鎖状又は脂環式のハロゲン化炭化水素基である。ｉは、０又は１である。ｊは、１〜１０の整数である。ｊが２以上の場合、複数のＲ^１６は、同一であっても異なっていてもよい。〕

[In Formula (2-4), R ¹⁵ and R ¹⁶ are each independently a divalent chain or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a divalent group having 1 to 20 carbon atoms. A chain or alicyclic halogenated hydrocarbon group. i is 0 or 1. j is an integer of 1-10. When j is 2 or more, the plurality of R ¹⁶ may be the same or different. ]

For R ¹⁵ and R ¹⁶ in the formula (2-4), all the explanations regarding R ¹³ in the formula (2-3) can be applied as they are. j is preferably 0 to 5, more preferably 0 to 3, from the viewpoint of improving the polymerization reactivity of the monomer that gives the second structural unit.

  Further, examples of the divalent organic group represented by X in the formula (2) include groups represented by the following formula (2-5).

〔式（２−５）中、Ｒ^２１及びＲ^２２は、それぞれ独立して、ハロゲン原子、炭素数１〜２０の１価の炭化水素基、炭素数１〜２０の１価のハロゲン化炭化水素基、炭素数１〜２０のアルコキシ基、炭素数１〜２０のアルキルチオ基、ニトロ基、シアノ基、カルボキシ基、スルホン酸基、ホスホン酸基、リン酸基、ヒドロキシ基、１〜３級アミノ基、カルボキシ基の塩、スルホン酸基の塩、ホスホン酸基の塩、リン酸基の塩、ヒドロキシ基の塩、又は１〜３級アミノ基の塩である。ｋ及びｌは、それぞれ独立して、０〜３の整数である。ｋが２又は３の場合、複数のＲ^２１は、同一であっても異なっていてもよい。ｌが２又は３の場合、複数のＲ^２２は、同一であっても異なっていてもよい。Ｒ^２３は、単結合、−Ｏ−、−Ｓ−、−Ｃ（Ｏ）−、−Ｓ（Ｏ）−、又は、−Ｓ（Ｏ）_２−である。〕

[In Formula (2-5), R ²¹ and R ²² are each independently a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent halogenated hydrocarbon having 1 to 20 carbon atoms. Group, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, a nitro group, a cyano group, a carboxy group, a sulfonic acid group, a phosphonic acid group, a phosphoric acid group, a hydroxy group, and a primary to tertiary amino group. A salt of a carboxy group, a salt of a sulfonic acid group, a salt of a phosphonic acid group, a salt of a phosphoric acid group, a salt of a hydroxy group, or a salt of a primary to tertiary amino group. k and l are each independently an integer of 0 to 3. When k is 2 or 3, the plurality of R ²¹ may be the same or different. When l is 2 or 3, the plurality of R ²² may be the same or different. R ²³ is a single bond, —O—, —S—, —C (O) —, —S (O) —, or —S (O) ₂ —. ]

For R ²¹ and R ²² in Formula (2-5), all the descriptions regarding R ⁴ in Formula (2-1) can be applied as they are. In the formula (2-5), k and l are each preferably 0 to 2, more preferably 0 to 1, from the viewpoint of improving the polymerization reactivity of the monomer that gives the second structural unit.

  Further, examples of the divalent organic group represented by X in the formula (2) include groups represented by the following formula (2-6).

〔式（２−６）中、Ｒ^２４及びＲ^２５は、それぞれ独立して、ハロゲン原子、炭素数１〜２０の１価の炭化水素基、炭素数１〜２０の１価のハロゲン化炭化水素基、炭素数１〜２０のアルコキシ基、炭素数１〜２０のアルキルチオ基、ニトロ基、シアノ基、カルボキシ基、スルホン酸基、ホスホン酸基、リン酸基、ヒドロキシ基、１〜３級アミノ基、カルボキシ基の塩、スルホン酸基の塩、ホスホン酸基の塩、リン酸基の塩、ヒドロキシ基の塩、又は１〜３級アミノ基の塩である。ｍ及びｎは、それぞれ独立して、０〜３の整数である。ｍが２又は３の場合、複数のＲ^２４は、同一であっても異なっていてもよい。ｎが２以上の場合、複数のＲ^２５は、同一であっても異なっていてもよい。Ｒ^２６及びＲ^２７は、それぞれ独立して、単結合、−Ｏ−、−Ｓ−、−Ｃ（Ｏ）−、−Ｓ（Ｏ）−、又は、−Ｓ（Ｏ）_２−である。〕

[In Formula (2-6), R ²⁴ and R ²⁵ are each independently a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent halogenated hydrocarbon having 1 to 20 carbon atoms. Group, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, a nitro group, a cyano group, a carboxy group, a sulfonic acid group, a phosphonic acid group, a phosphoric acid group, a hydroxy group, and a primary to tertiary amino group. A salt of a carboxy group, a salt of a sulfonic acid group, a salt of a phosphonic acid group, a salt of a phosphoric acid group, a salt of a hydroxy group, or a salt of a primary to tertiary amino group. m and n are each independently an integer of 0 to 3. When m is 2 or 3, the plurality of R ²⁴ may be the same or different. When n is 2 or more, the plurality of R ²⁵ may be the same or different. R ²⁶ and R ²⁷ are each independently a single bond, —O—, —S—, —C (O) —, —S (O) —, or —S (O) ₂ —. ]

With respect to R ²⁴ and R ²⁵ in the formula (2-6), all the descriptions regarding R ⁴ in the formula (2-1) can be applied as they are. M and n in Formula (2-6) are each preferably 0 to 2, more preferably 0 to 1, from the viewpoint of improving the polymerization reactivity of the monomer that gives the second structural unit.

  Further, examples of the divalent organic group represented by X in the above formula (2) include groups represented by the following formula (2-7).

〔式（２−７）中、Ｒ^２８及びＲ^２９は、それぞれ独立して、ハロゲン原子、炭素数１〜２０の１価の炭化水素基、炭素数１〜２０の１価のハロゲン化炭化水素基、炭素数１〜２０のアルコキシ基、炭素数１〜２０のアルキルチオ基、ニトロ基、シアノ基、カルボキシ基、スルホン酸基、ホスホン酸基、リン酸基、ヒドロキシ基、１〜３級アミノ基、カルボキシ基の塩、スルホン酸基の塩、ホスホン酸基の塩、リン酸基の塩、ヒドロキシ基の塩、又は１〜３級アミノ基の塩である。ｏは、０〜３の整数である。ｐは、０〜４の整数である。ｏが２以上の場合、複数のＲ^２８は、同一であっても異なっていてもよい。ｐが２以上の場合、複数のＲ^２９は、同一であっても異なっていてもよい。ｎは、０〜６の整数である。Ｒ^３０は、炭素数１〜２０の１価の炭化水素基、又は炭素数１〜２０の１価のハロゲン化炭化水素基である。ｑは、０〜１５の整数である。ｑが２以上の場合、複数のＲ^３０は、同一であっても異なっていてもよい。〕

[In Formula (2-7), R ²⁸ and R ²⁹ each independently represent a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent halogenated hydrocarbon having 1 to 20 carbon atoms. Group, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, a nitro group, a cyano group, a carboxy group, a sulfonic acid group, a phosphonic acid group, a phosphoric acid group, a hydroxy group, and a primary to tertiary amino group. A salt of a carboxy group, a salt of a sulfonic acid group, a salt of a phosphonic acid group, a salt of a phosphoric acid group, a salt of a hydroxy group, or a salt of a primary to tertiary amino group. o is an integer of 0-3. p is an integer of 0-4. When o is 2 or more, the plurality of R ²⁸ may be the same or different. When p is 2 or more, the plurality of R ²⁹ may be the same or different. n is an integer of 0-6. R ³⁰ is a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms. q is an integer of 0-15. When q is 2 or more, the plurality of R ³⁰ may be the same or different. ]

With respect to R ²⁸ and R ²⁹ in Formula (2-7), all the descriptions regarding R ⁴ in Formula (2-1) can be applied as they are. From the viewpoint of improving the polymerization reactivity of the monomer that gives the second structural unit, o and p in formula (2-7), respectively.
0-2 are preferable, More preferably, it is 0-1.

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R ³⁰ in formula (2-7) include those represented by R ¹ in formulas (1-1) to (1-3) above. Examples thereof include monovalent hydrocarbon groups having 1 to 20 carbon atoms exemplified as the groups.

Examples of the monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms represented by R ³⁰ include the groups represented by R ¹ in the above formulas (1-1) to (1-3). Examples include a group in which part or all of the hydrogen atoms of a monovalent hydrocarbon group having 1 to 20 carbon atoms are substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

R ³⁰ is a hydrogen atom, a monovalent hydrocarbon group having 1 to 3 carbon atoms, or a monovalent hydrocarbon group having 1 to 3 carbon atoms from the viewpoint of improving the polymerization reactivity of the monomer that gives the second structural unit. Halogenated hydrocarbon groups are preferred. From the same viewpoint, n is preferably 0 to 4, more preferably 0 to 2. From the same viewpoint, q is preferably 0 to 11, more preferably 0 to 7.

  Furthermore, examples of the divalent organic group represented by X in the above formula (2) include groups represented by the following formula (2-8).

〔式（２−８）中、Ｒ^３１及びＲ^３２は、それぞれ独立して、ハロゲン原子、炭素数１〜２０の１価の炭化水素基、炭素数１〜２０の１価のハロゲン化炭化水素基、炭素数１〜２０のアルコキシ基、炭素数１〜２０のアルキルチオ基、ニトロ基、シアノ基、カルボキシ基、スルホン酸基、ホスホン酸基、リン酸基、ヒドロキシ基、１〜３級アミノ基、カルボキシ基の塩、スルホン酸基の塩、ホスホン酸基の塩、リン酸基の塩、ヒドロキシ基の塩、又は１〜３級アミノ基の塩である。ｒ及びｓは、それぞれ独立して、０〜４の整数である。ｒが２以上の場合、複数のＲ^３１は、同一であっても異なっていてもよい。ｓが２以上の場合、複数のＲ^３２は、同一であっても異なっていてもよい。ｍは、１〜５の整数である。ｎは、０〜５の整数である。Ｒ^３３は、炭素数１〜２０の１価の炭化水素基、又は炭素数１〜２０の１価のハロゲン化炭化水素基である。ｔは、０〜２０の整数である。ｔが２以上の場合、複数のＲ^３３は、同一であっても異なっていてもよい。〕

[In Formula (2-8), R ³¹ and R ³² are each independently a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent halogenated hydrocarbon having 1 to 20 carbon atoms. Group, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, a nitro group, a cyano group, a carboxy group, a sulfonic acid group, a phosphonic acid group, a phosphoric acid group, a hydroxy group, and a primary to tertiary amino group. A salt of a carboxy group, a salt of a sulfonic acid group, a salt of a phosphonic acid group, a salt of a phosphoric acid group, a salt of a hydroxy group, or a salt of a primary to tertiary amino group. r and s are each independently an integer of 0 to 4. When r is 2 or more, the plurality of R ³¹ may be the same or different. When s is 2 or more, the plurality of R ³² may be the same or different. m is an integer of 1-5. n is an integer of 0-5. R ³³ is a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms. t is an integer of 0-20. When t is 2 or more, the plurality of R ³³ may be the same or different. ]

For R ³¹ and R ³² in Formula (2-8), all the descriptions regarding R ⁴ in Formula (2-1) can be applied as they are. r and s are preferably 0 to 2 and more preferably 0 to 1 from the viewpoint of improving the polymerization reactivity of the monomer that gives the second structural unit. From the same viewpoint, m is preferably 1 to 3, and more preferably 1 to 2. In addition, from the same viewpoint, n is preferably 0 to 3, more preferably 0 to 2.

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R ³³ in formula (2-8) include those represented by R ¹ in the above formulas (1-1) to (1-3). Examples thereof include monovalent hydrocarbon groups having 1 to 20 carbon atoms exemplified as the groups.

Examples of the monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms represented by R ³³ are the groups represented by R ¹ in the above formulas (1-1) to (1-3). Examples include a group in which part or all of the hydrogen atoms of a monovalent hydrocarbon group having 1 to 20 carbon atoms are substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

R ³³ is a hydrogen atom, a monovalent hydrocarbon group having 1 to 3 carbon atoms, or a monovalent hydrocarbon group having 1 to 3 carbon atoms from the viewpoint of improving the polymerization reactivity of the monomer that gives the second structural unit. Halogenated hydrocarbon groups are preferred. From the same viewpoint, t is preferably 0 to 12, and more preferably 0 to 8.

  Furthermore, as a bivalent organic group represented by said X of said Formula (2), a C1-C20 bivalent hydrocarbon group is mentioned. Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms include a divalent chain hydrocarbon group, a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and 2 having 6 to 20 carbon atoms. Valent aromatic hydrocarbon group and the like.

Examples of the divalent chain hydrocarbon group include divalent chain hydrocarbon groups having 1 to 20 carbon atoms exemplified as the group represented by R ¹³ in the formula (2-3). It is done. Examples of the divalent alicyclic hydrocarbon group, for example, a divalent alicyclic hydrocarbon group exemplified C3-20 group represented by the R ¹³ in the formula (2-3) or the like Is mentioned. Examples of the divalent aromatic hydrocarbon group include arylene groups such as a phenylene group, a tolylene group, a naphthylene group, and an anthrylene group.

  When the divalent organic group represented by X is a divalent hydrocarbon group having 1 to 20 carbon atoms, from the viewpoint of improving the polymerization reactivity of the monomer that gives the second structural unit, the carbon number is 1 A divalent chain hydrocarbon group having ˜16, a divalent alicyclic hydrocarbon group having 3 to 10 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms is preferable.

  Furthermore, as a bivalent organic group represented by said X of said Formula (2), a C1-C20 bivalent halogenated hydrocarbon group etc. are mentioned. Examples of the divalent halogenated hydrocarbon group having 1 to 20 carbon atoms include part or all of the hydrogen atoms in the divalent hydrocarbon group having 1 to 20 carbon atoms exemplified as the group represented by X above. And a group in which a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom is substituted.

  In the case where the divalent organic group represented by X is a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, from the viewpoint of improving the polymerization reactivity of the monomer giving the second structural unit, carbon A chain halogenated hydrocarbon group having 1 to 16 carbon atoms, an alicyclic halogenated hydrocarbon group having 3 to 10 carbon atoms, or a halogenated aromatic hydrocarbon group having 6 to 20 carbon atoms is preferable.

Furthermore, examples of the divalent organic group represented by X in the formula (2) include divalent heterocyclic groups having 3 to 10 ring members. Examples of the divalent heterocyclic group having 3 to 10 ring members include pyrazine, pyrimidine, pyritazine, triazine, pyrrole, 2H-pyrrole, imidazole, pyrazole, isothiazole, isoxazole, pyridine, pyrazine, pyrimidine, pyridazine, Indolizine, isoindole, 3H-indole, indole, 1H-indazole, purine, 4H-quinolidine, quinoline, isoquinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, carbazole, carboline, phenanthridine, acridine, perimidine, Phenanthroline, phenazine, phenothiazine, furazane, phenoxazine, pyrrolidine, pyrroline, imidazoline, imidazolidine, pyrazolidine, pyrazoline, piperidine, piper Containing azine, indoline, isoindoline, quinuclidine, oxazole, benzoxazole, 1,3,5-triazine, bromine, tetrazole, tetrazine, triazole, phenalsazine, benzimidazole, benzotriazole, thiazole, benzothiazole, thiadiazole, benzothiadiazole, etc. Examples include a group obtained by removing two hydrogen atoms from a nitrogen heterocyclic compound.

Moreover, the hydrogen atom in this heterocyclic group is a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. An alkylthio group having 1 to 20 carbon atoms, a nitro group, a cyano group, a carboxy group, a sulfonic acid group, a phosphonic acid group, a phosphoric acid group, a hydroxy group, a primary to tertiary amino group, a salt of a carboxy group, a sulfonic acid group It may be substituted with a salt, a salt of a phosphonic acid group, a salt of a phosphoric acid group, a salt of a hydroxy group, or a salt of a primary to tertiary amino group. Note that these substituents can be applied to the description of R ⁴ in the formula (2-1).

  When the divalent organic group represented by X is a divalent heterocyclic group having 3 to 10 ring members, from the viewpoint of improving the polymerization reactivity of the monomer that gives the second structural unit, the number of ring members is 3 10 to 10 divalent nitrogen-containing heterocyclic groups are preferable.

  [A] The second structural unit in the polymer is preferably a structural unit represented by the formula (2). In particular, from the viewpoint of further improving the heat resistance, X in the formula (2) is a group represented by the above formulas (2-1) to (2-4), or a divalent valence having 1 to 20 carbon atoms. Is preferably a hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, or a divalent heterocyclic group having 3 to 10 ring members. It is more preferably a group represented by the formula (2-1), a group represented by the above formula (2-2), or a divalent heterocyclic group having 3 to 10 ring members.

Moreover, as a monomer which gives the 2nd structural unit in a [A] polymer, the compound etc. which are represented by the following formula (M-1)-(M-66) are mentioned, for example. These monomers may be used individually by 1 type, and may use 2 or more types together. In the following formulas (M-1) to (M-66), A is —OH, —SH, —NH ₂ , or —N (R ³⁵ ) H. R ³⁵ is a monovalent hydrocarbon group having 1 to 20 carbon atoms. Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include monovalent hydrocarbons having 1 to 20 carbon atoms exemplified as groups represented by R ¹ in the above formulas (1-1) to (1-3). And the like. Moreover, several A in each compound may respectively be the same, and may differ.

When said [A] polymer is provided with the said 1st and 2nd structural unit, it may have only 1 type of each structural unit, and may have 2 or more types. [A] The polymer may have a repeating unit (a), (b) or (c) containing the first and second structural units as described later, and further has other repeating units. May be.

  [A] The lower limit of the content ratio of the first structural unit in the polymer is preferably 5 mol%, more preferably 10%, when the total of all structural units in the [A] polymer is 100 mol%. The mol%, more preferably 20 mol%, particularly preferably 33 mol%. Further, the upper limit of the content is preferably 95 mol%, more preferably 67 mol%, still more preferably 60 mol%, and particularly preferably 50 mol%. By making the said content rate into the said range, the toughness of a hardened | cured material, heat resistance, and chemical resistance can be improved more.

  When the [A] polymer has the second structural unit, the lower limit of the content ratio of the second structural unit is 5 mol% when the total of all the structural units in the [A] polymer is 100 mol%. It is preferably 10 mol%, more preferably 10 mol%, still more preferably 20 mol%, particularly preferably 33 mol%. Further, the upper limit of the content is preferably 95 mol%, more preferably 67 mol%, still more preferably 60 mol%, and particularly preferably 50 mol%. By making the said content rate into the said range, the toughness of a hardened | cured material, heat resistance, and chemical resistance can be improved more.

(Other structural units)
The [A] polymer may have another structural unit different from the second structural unit, for example, for the purpose of adjusting the molecular weight or the like, as long as the effects described above are not impaired. [A] When the polymer contains other structural units, the lower limit of the total content of other structural units is 1 when the total of all structural units in the [A] polymer is 100 mol%. It is preferably a mol%, more preferably 5 mol%, still more preferably 10 mol%. Moreover, it is preferable that the upper limit of the said content rate is 40 mol%, More preferably, it is 30 mol%. By making the said content rate into the said range, adjustment of molecular weight can be easily performed in the range which does not impair the effect mentioned above.

(Array of each structural unit)
[A] As long as the polymer has the first structural unit, the arrangement of the structural unit is not limited, but from the viewpoint of further improving the toughness, heat resistance, and chemical resistance of the cured product, It is preferable to have two structural units in the main chain. Here, the “main chain” refers to the relatively long bond chain in the polymer.

(Repeat unit)
[A] Examples of the polymer having the first and second structural units in the main chain include, for example, a repeating unit (a) represented by the following formula (a), a repeating unit (b) represented by the following formula (b), The polymer which has the repeating unit (c) shown in following formula (c), the combination of these repeating units, etc. in a principal chain is mentioned.

In said formula (a)-(c), R < ¹ > and n are synonymous with R < ¹ > and n in said formula (1-1)-(1-3), respectively. A ¹ and ^{A 2,} respectively, the same meanings as ^{A 1} and ^{A 2} in the formula (2).

([A] Polymer content ratio)
In the composition of the present invention, the content ratio of the [A] polymer when the curable compound and the [A] polymer are 100% by mass is, for example, preferably from 1% by mass to 99% by mass, More preferably, they are 5 mass% or more and 95 mass% or less, More preferably, they are 10 mass% or more and 90 mass% or less. When this content rate exists in the said range, it is preferable from a viewpoint of improving the toughness of a hardened | cured material, heat resistance, and chemical resistance more.

([A] Polymer Synthesis Method)
The method for synthesizing the [A] polymer in the present invention is not particularly limited. For example, a monomer that provides the first structural unit, a monomer that provides the second structural unit, and other compounds as necessary. It can be synthesized by reacting in an organic solvent under predetermined conditions.

  Examples of the other compounds include terminal terminators such as alkali metal compounds and monofunctional phenols, and monomers that give other structural units.

  Examples of the alkali metal compound include alkali metal hydrides such as lithium hydride, sodium hydride and potassium hydride; alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; lithium carbonate and sodium carbonate And alkali metal carbonates such as potassium carbonate; alkali metal hydrogen carbonates such as lithium hydrogen carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate. Among these, alkali metal hydroxides and alkali metal carbonates are preferable, and sodium hydroxide and potassium carbonate are more preferable.

  When the alkali metal compound is used, the lower limit of the amount used is preferably a 1-fold equivalent as the amount of metal atoms in the alkali metal compound relative to the hydroxyl groups of all monomers used in the synthesis of the polymer [A]. The 1-fold equivalent is more preferred, the 1.2-fold equivalent is more preferred, and the 1.5-fold equivalent is particularly preferred. On the other hand, the upper limit of the amount used is preferably 3 times equivalent and more preferably 2 times equivalent.

  Examples of the organic solvent include N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, γ-butyrolactone, sulfolane, and dimethyl sulfoxide. , Diethyl sulfoxide, dimethyl sulfone, diethyl sulfone, diisopropyl sulfone, diphenyl sulfone, diphenyl ether, benzophenone, methylene chloride, benzene, toluene, xylene, dialkoxybenzene (1 to 4 carbon atoms of alkoxy group), trialkoxybenzene (alkoxy group of C1-C4) etc. are mentioned. In addition, these organic solvents may be used individually by 1 type, and may use 2 or more types together.

  In addition to the organic solvents exemplified above, azeotropic solvents such as hexane, cyclohexane, octane, chlorobenzene, dioxane, tetrahydrofuran, anisole, and phenetole can be used in combination. In addition, these solvent may be used individually by 1 type, and may use 2 or more types together.

  [A] The reaction temperature during the synthesis of the polymer is, for example, 20 ° C. or higher and 250 ° C. or lower. The reaction time is, for example, 15 minutes or more and 100 hours or less. [A] The polymer can be obtained as a solution, powder or pellet. When it is obtained as a powder, it is obtained by coagulation in a poor solvent, and after filtration, washing and drying. In that case, it is coagulated after pretreatment with an aqueous solution or solvent containing an alkali metal compound or ammonia. May be. Alternatively, it can also be obtained by directly coagulating with an aqueous solution or a poor solvent containing an alkali metal compound or ammonia.

([A] Weight average molecular weight of polymer (Mw))
[A] The lower limit of the weight average molecular weight (Mw) of the polymer is preferably 500, more preferably 1,000, still more preferably 5,000, still more preferably 10,000, and most preferably 30,000. 000. The upper limit of Mw is preferably 600,000, more preferably 400,000, still more preferably 300,000, and most preferably 200,000. Heat resistance can be improved more by making said Mw more than the said minimum. On the other hand, when the Mw exceeds the upper limit, the viscosity becomes too high, and the applicability and operability may be reduced.

([A] Glass transition temperature (Tg) of polymer)
[A] As a minimum of glass transition temperature (Tg) of a polymer, 150 ° C is preferred and 180 ° C is more preferred. Although the upper limit of the said glass transition temperature is not specifically limited, For example, 320 degreeC is preferable and 300 degreeC is more preferable. Heat resistance can be improved more by making the said glass transition temperature more than the said minimum. In addition, this glass transition temperature can be made into the value measured with the temperature increase rate of 20 degree-C / min in nitrogen atmosphere, for example using the differential scanning calorimeter.

[Curable compound]
The curable compound in the present invention is a compound that is cured by irradiation with heat or light (for example, visible light, ultraviolet ray, near infrared ray, far infrared ray, electron beam, etc.) and requires a curing aid described later. May be. Examples of such curable compounds include epoxy compounds, cyanate ester compounds, vinyl compounds, silicone compounds, oxazine compounds, maleimide compounds, allyl compounds, acrylic compounds, methacrylic compounds, and urethane compounds. These may be used alone or in combination of two or more. Among them, at least one of epoxy compounds, cyanate ester compounds, vinyl compounds, silicone compounds, oxazine compounds, maleimide compounds, and allyl compounds from the viewpoint of properties such as compatibility with [A] polymer and heat resistance. It is preferably a seed, and particularly preferably at least one of an epoxy compound, a cyanate ester compound, a vinyl compound, an allyl compound, and a silicone compound.

  Examples of the epoxy compound include compounds represented by the following formulas (c1-1) to (c1-6) [wherein the compound represented by (c1-6) is “XER-81”. (This is an epoxy-containing NBR particle manufactured by JSR). Furthermore, polyglycidyl ether of dicyclopentadiene / phenol polymer, phenol novolac type liquid epoxy, epoxidized product of styrene-butadiene block copolymer, 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate Etc.

  Examples of the cyanate ester compound include compounds represented by the following formulas (c2-1) to (c2-7).

  Examples of the vinyl compound include compounds represented by the following formulas (c3-1) to (c3-5).

Examples of the silicone compound include compounds represented by the following formulas (c4-1) to (c4-16). In addition, as R in Formula (c4-1), when any one of the following is selected and a compound having a vinyl group is selected, it can be handled as the vinyl compound. In formulas (c4-2) to (c4-16), each R is independently an organic group selected from an alkyl group, a cycloalkyl group, an aryl group, and an alkenyl group, and n is 0 to 1000. An integer (preferably an integer of 0 to 100). Examples of the alkyl group, the cycloalkyl group, the aryl group, and the alkenyl group include those exemplified in the description of R ^{1 in} the above formula (1-1).

  Examples of the oxazine compound include compounds represented by the following formulas (c5-1) to (c5-5).

  Examples of the maleimide compound include compounds represented by the following formulas (c6-1) to (c6-5).

  Examples of the allyl compound include compounds represented by the following formulas (c7-1) to (c7-6). In particular, the allyl compound is preferably a compound having two or more (particularly 2 to 6, more preferably 2 to 3) allyl groups.

(Content ratio of curable compound)
The content of the curable compound in the composition of the present invention is preferably 0.05% by mass or more and 99.95% by mass or less, more preferably 10%, for example, when the entire composition is 100% by mass. It is 20 mass% or more and 80 mass% or less more preferably 20 mass% or more. When this content rate exists in the said range, it is preferable from a viewpoint of improving the toughness of a hardened | cured material, heat resistance, and chemical resistance more. Moreover, when the sum total of a curable compound and a [A] polymer is 100 mass%, it is preferable that the content rate of a curable compound is 1 to 99 mass%, More preferably, it is 5 mass%. It is 95 mass% or less, More preferably, it is 10 mass% or more and 90 mass% or less. When this content rate exists in the said range, it is preferable from a viewpoint of improving the toughness of a hardened | cured material, heat resistance, and chemical resistance more.

[Curing aid]
The composition in the present invention may contain a curing aid as necessary. As said hardening adjuvant, polymerization initiators, such as a hardening | curing agent and a photoreaction initiator (a photoradical generator, a photoacid generator, a photobase generator), can be mentioned, for example. These curing assistants may be used alone or in combination of two or more, regardless of the type.

  Examples of the curing aid in the case where an epoxy compound is used as the curable compound include amine-based curing agents, acid or acid anhydride-based curing agents, basic active hydrogen compounds, imidazoles, polymercaptan-based curing agents, and phenols. A curing agent such as a resin, a urea resin, a melamine resin, an isocyanate curing agent, or a Lewis acid can be used.

Examples of the amine curing agent include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, iminobispropylamine, bis (hexamethylene) triamine, 1,3,6-trisaminomethylhexane, and the like. Polymethylenediamines such as trimethylhexamethylenediamine, polyetherdiamine, diethylaminopropylamine, etc .; mensendiamine (MDA), isophoronediamine (IPDA), bis (4-amino-3-methylcyclohexyl) methane, diaminodicyclohexyl Methane, bisaminomethylcyclohexane, 3,9
-Cyclic aliphatic polyamines such as bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, diamine having a norbornane skeleton represented by NBDA manufactured by Mitsui Chemicals, Inc .; Aliphatic polyamines containing aromatic rings such as metaxylylenediamine (MXDA); aromatic polyamines such as metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiethyldiphenylmethane, and derivatives thereof.

  Furthermore, as other amine-based curing agents, for example, Mannich modified diamine obtained by reacting polyamine with aldehyde and / or phenol; amine adduct (polyamine epoxy resin adduct), polyamine-ethylene oxide adduct, polyamine-propylene oxide adduct, Ketimine which is a reaction product of cyanoethylated polyamine, aliphatic polyamine and ketone; tetramethylguanidine, triethanolamine, piperidine, pyridine, benzyldimethylamine, picoline, 2- (dimethylaminomethyl) phenol, dimethylcyclohexylamine, dimethylbenzyl Amine, dimethylhexylamine, dimethylaminophenol, dimethylamino-p-cresol, N, N′-dimethylpiperazine, 1,4-diazadisi Secondary amines such as b [2.2.2] octane, 2,4,6-tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo [5.4.0] -7-undecene, or tertiary Secondary amines; liquid polyamides obtained by reacting dimer acids with polyamines such as diethylenetriamine and triethylenetetramine.

  Examples of the acid or acid anhydride curing agent include polycarboxylic acids such as adipic acid, azelaic acid, and decanedicarboxylic acid; phthalic anhydride, trimellitic anhydride, ethylene glycol bis (anhydrotrimellitate), glycerol Aromatic acid anhydrides such as tris (andro trimellitate), pyromellitic anhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid anhydride; maleic anhydride, succinic anhydride, tetrahydrophthalic anhydride , Methyltetrahydrophthalic anhydride, methylnadic anhydride, alkenyl succinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylcyclohexenetetracarboxylic anhydride, methylhymic anhydride, trialkyltetrahydrophthalic anhydride, Poly (phenylhexadecane ) Cyclic aliphatic acid anhydrides such as anhydrides; Aliphatic acid anhydrides such as polyadipic acid anhydrides, polyazeline acid anhydrides, polysebacic acid anhydrides, dodecenyl succinic acid anhydrides, poly (ethyloctadecandioic acid) anhydrides; Examples thereof include halogenated acid anhydrides such as chlorendic acid anhydride, tetrabromophthalic anhydride, and het anhydride.

  Examples of the basic active hydrogen compound include dicyandiamide and organic acid dihydrazide.

  Examples of the imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1- Cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-methylimidazolium isocyanurate, 2,4-diamino-6- [2-methylimidazoline- (1)]-ethyl-S -Triazine, 2,4-diamino-6- [2-ethyl-4-methylimidazoline- (1)]-ethyl-S-triazine and the like.

  Examples of the polymercaptan-based curing agent include partial epoxy adducts of 2,2′-bismercaptoethyl ether; pentaerythritol tetrathioglycolate, dipentaerythritol hexathioglycolate, trimethylolpropane tristhioglycolate, and the like. Thioglycolic acid esters; compounds containing mercapto groups such as polysulfide rubbers having mercapto groups at the ends.

  Examples of the isocyanate curing agent include isocyanate compounds such as toluene diisocyanate, hexamethylene diisocyanate, and xylene diisocyanate; blocked isocyanate compounds formed by reacting an isocyanate group with a blocking agent such as phenol, alcohol, and caprolactam, and the like. Is mentioned.

  Examples of the Lewis acid include diallyl iodonium salt and triallyl sulfonium salt.

  In this case, the curing aids include onium salt compounds, sulfone compounds, sulfonic acid ester compounds, sulfonimide compounds, disulfonyldiazomethane compounds, disulfonylmethane compounds, oxime sulfonate compounds, hydrazine sulfonate compounds, triazine compounds, nitrobenzyl. In addition to compounds, photoacid generators such as organic halides and disulfone can be used.

  Furthermore, as a curing aid in this case, (Z)-{[bis (dimethylamino) methylidene] amino} -N-cyclohexyl (cyclohexylamino) methaniminium tetrakis (3-fluorophenyl) borate ((Z)- {[Bis (dimethylamino) methylidene] amino} -N-cyclohexyl (cyclohexylamino) tetrakis (3-fluorophenyl) borate), 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidinium Phenyl borate, 9-anthrylmethyl N, N-diethylcarbamate, (E) -1- [3- (2-hydroxyphenyl) -2-propenoyl] piperidine ((E) -1- [3- (2-hydroxyphenyl) -2-propenoyl] piperidine)), 1- (anthraquinone-2-yl) Ethyl imidazole carboxylate (1- (anthraquinon-2-yl) ethyl imidazoleboxylate), 2-nitrophenylmethyl 4-methacryloyloxypiperidine-1-carboxylate, 1,2-diisopropyl-3- [bis (dimethylamino) methylene] Photobase generators such as guanidinium 2- (3-benzoylphenyl) propionate can be used.

  Curing aids when cyanate ester compounds are used as the curable compounds include tertiary amines such as octanoic acid, stearic acid, acetylacetonate, naphthenic acid, salicylic acid, 2-ethyl-4-imidazole, 4-methyl Curing agents such as imidazoles such as imidazole can be used. Furthermore, the photoacid generator and the photobase generator described as the curing aid when the epoxy compound is used can be used.

Examples of the curing aid when a vinyl compound is used as the curable compound include a compound that generates a cation or a radical active species by heat or light. Examples of the cationic polymerization agent include diallyl iodonium salts and triallyl sulfonium salts. Examples of radical polymerization agents include benzoin-based compounds such as benzoin acetophenone, acetophenone-based compounds such as 2,2-dimethoxy-2-phenylacetophenone, sulfur-based compounds such as 2,4-diethylthioxanthone, and azobisisobitylnitrile. Examples thereof include organic peroxides such as azo compounds, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, and dicumyl peroxide. Also, acetophenone, propiophenone, benzophenone, xanthol, benzaldehyde, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-methylacetophenone, 3-pentylacetophenone, 4-methoxyacetophene, 3-bromoacetophenone, 4 -Allyl acetophenone, p-diacetylbenzene, 3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4-chloro-4
'-Benzylbenzophenone, 3-chloroxanthone, 3,9-dichloroxanthone, 3-chloro-8-nonylxanthone, benzoyl, benzoin methyl ether, benzoin butyl ether, bis (4-dimethylaminophenyl) ketone, benzylmethoxy Photo radical generators such as ketal and 2-chlorothioxanthone can be used.

  As a curing aid when a silicone compound is used as the curable compound, zinc benzoate, zinc octylate, platinum black, platinous chloride, chloroplatinic acid, a reaction product of chloroplatinic acid and a monohydric alcohol, Curing agents such as complexes of chloroplatinic acid and olefins, platinum-based catalysts such as platinum bisacetoacetate; palladium-based catalysts; rhodium-based catalysts; and the like can be used. Also, acetophenone, propiophenone, benzophenone, xanthol, benzaldehyde, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-methylacetophenone, 3-pentylacetophenone, 4-methoxyacetophenone, 3-bromoacetophenone, 4- Allyl acetophenone, p-diacetylbenzene, 3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 2,2′-diethoxyacetophenone, 4-chloro-4′-benzylbenzophenone, 3-chloroxanthone, 3,9-dichloroxanthone, 3-chloro-8-nonylxanthone, benzoin, benzoin methyl ether, benzoin butyl ether Bis (4-dimethylaminophenyl) ketone, benzylmethoxyketal, 2-chlorothioxanthone, diethylacetophenone, 1-hydroxycyclohexyl phenylketone, 2-methyl-1 {4- (methylthio) phenyl} -2-morpholino- 1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1-one, 1- {4- (2-hydroxyethoxy) -phenyl} -2-methyl-1- Photoinitiators such as propan-1-one, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and cyclohexyl phenyl ketone can be used. .

  In the case where an oxazine compound is used as the curable compound, as a curing aid, phenol and derivatives thereof, cyanate ester, Bronsted acid such as p-toluenesulfonic acid, adipic acid, p-toluenesulfonic acid ester, Aromatic amine compounds such as 4,4′-diaminodiphenylsulfone and melamine, bases such as 2-ethyl-4-methylimidazole, and curing agents such as boron trifluoride and Lewis acid can be used. Furthermore, the photoacid generator and the photobase generator described as the curing aid when the epoxy compound is used can be used.

  Curing aids when a maleimide compound is used as the curable compound include imidazole, 1-methylimidazole, 1-benzyl-2-methylimidazole, 2-methylimidazoline, N, N-diisopropylethylamine, 1,4- Bases such as dimethylpiperazine, quinoline, triazole, benzotriazole, DBU, phosphorus compounds such as triphenylphosphine, and curing agents such as azobisisobutylnitrile can be used. Furthermore, the photoacid generator and the photobase generator described as the curing aid when the epoxy compound is used can be used.

Curing aids when an allyl compound is used as the curable compound include azo initiators such as azobisisobutyronitrile and dimethyl 2,2′-azobisisobutyrate, ketone peroxide, peroxyketal, and hydroperoxide. , Peroxides such as dialkyl peroxide, diacyl peroxide, peroxydicarbonate, peroxyester, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1,1′-hydroxycyclohexyl Acetophenones such as phenyl ketone, benzoins such as benzoin and benzoin ethyl ether, benzophenones such as benzophenone,
Curing agents such as phosphorus series such as acylphosphine oxide, sulfur series such as thioxanthone series, benzyl series such as benzyl, 9,10-phenanthrenequinone, and peroxycarbonate series can be used. Furthermore, the photoacid generator and the photobase generator described as the curing aid when the epoxy compound is used can be used.

(Content ratio of curing aid)
When the resin composition in this invention contains a hardening adjuvant, the content rate of this hardening adjuvant should just be a range which this composition hardens | cures favorably and hardened | cured material is obtained. For example, the amount is preferably 5 parts by mass or more and 20 parts by mass or less, and more preferably 5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the total of [A] polymer and curable compound.

[solvent]
The composition in the present invention may contain a solvent as necessary. Examples of the solvent include N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and 1,3-dimethyl-2-imidazolidinone. Amide solvents; ester solvents such as γ-butyrolactone and butyl acetate; ketone solvents such as cyclopentanone, cyclohexanone, methyl ethyl ketone, and benzophenone; ether solvents such as 1,2-methoxyethane and diphenyl ether; 1-methoxy-2 -Polyfunctional solvents such as propanol and propylene glycol methyl ether acetate; sulfolane solvents such as sulfolane, dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, diethyl sulfone, diisopropyl sulfone, and diphenyl sulfone; Zen, toluene, xylene, dialkoxybenzenes (the number of carbon atoms in the alkoxy group; 1-4), (the number of carbon atoms in the alkoxy group; 1-4) trialkoxy benzene. These solvents may be used alone or in combination of two or more.

(Solvent content)
Although the content rate of the said solvent is not specifically limited, For example, 0 mass part or more and 2000 mass parts or less (especially 0 mass part or more and 200 mass parts or less) with respect to a total of 100 mass parts of [A] polymer and a curable compound In addition, when the solubility in an organic solvent is high, it can be 50 parts by mass or more and 100,000 parts by mass or less.

[Other ingredients]
The composition in the present invention may further contain other components as long as the effects of the present invention are not impaired. Examples of the other components include an antioxidant, a reinforcing agent, a lubricant, a flame retardant, an antibacterial agent, a colorant, a release agent, a foaming agent, and a polymer other than the [A] polymer. In addition, these other components may be used individually by 1 type, and may use 2 or more types together.

  Examples of the antioxidant include hindered phenol compounds, phosphorus compounds, sulfur compounds, metal compounds, hindered amine compounds, and the like. Of these, hindered phenol compounds are preferred.

As the hindered phenol compound, those having a molecular weight of 500 or more are preferable. Examples of hindered phenol compounds having a molecular weight of 500 or more include triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [ 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-tert-butylanilino) -3,5-triazine, pentaerythritol tetrakis [3- (3,5-t-butyl-4-hydroxyphenyl) propionate], 1,1,3-tris [2-methyl-4- [3- (3 5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -5-t-butylphenyl] butane, 2,2-thio-
Diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N- Hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl- 4-hydroxybenzyl) benzene, tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 3,9-bis [2- [3- (3-t-butyl-4-hydroxy -5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane and the like.

  When the composition in this invention contains antioxidant, the content rate of this antioxidant is 0.01 mass part or more and 10 with respect to a total of 100 mass parts of a [A] polymer and a sclerosing | hardenable compound, for example. It can be below mass parts.

[Method for Preparing Composition]
The method for preparing the composition in the present invention is not particularly limited. For example, [A] a polymer, a curable compound, and other additives as required (for example, a curing aid, a solvent, an antioxidant, etc. Can be prepared by mixing uniformly. The form of the composition can be liquid, pasty, or the like. In particular, since the [A] polymer in the present invention is excellent in solubility, a solvent-free composition can be obtained by dissolving it in a liquid curable compound.

<Hardened product>
The cured product of the present invention is obtained by curing the above-described composition of the present invention. The shape of the said hardened | cured material is not specifically limited, It can be set as a suitable shape according to a use, the objective, etc. Moreover, although the hardening method of a composition is not specifically limited, The method of thermosetting by heating and the method of photocuring by light irradiation are used normally. These methods can be used in combination. When thermosetting, the temperature is preferably 50 to 200 ° C, more preferably 100 to 200 ° C, and still more preferably 100 to 180 ° C. The heating time is preferably 0.5 to 36 hours, more preferably 0.5 to 24 hours. Moreover, when making it photocure, as light to irradiate, visible light, an ultraviolet-ray, a near infrared ray, a far infrared ray, an electron beam etc. are mentioned, for example.

<Laminated body>
The laminated body of this invention is equipped with a board | substrate and the hardened | cured material layer formed on this board | substrate using the composition of the above-mentioned this invention. Examples of the substrate include an inorganic substrate, a metal substrate, and a resin substrate from the viewpoint of adhesiveness and practical use. Examples of the inorganic substrate include inorganic substrates having silicon, silicon carbide, silicon nitride, alumina, glass, gallium nitride and the like as components. As said metal substrate, the metal substrate which uses copper, aluminum, gold | metal | money, silver, nickel, palladium etc. as a component is mentioned, for example. Examples of the resin substrate include substrates such as liquid crystal polymer, polyimide, polyphenylene sulfide, polyamide (nylon), polyethylene terephthalate, polyethylene naphthalate, and polyolefin.

  The cured product layer can be obtained by applying a composition on a substrate and then thermally curing or photocuring the composition. Although the thickness of a hardened | cured material layer is not specifically limited, For example, it can be referred to as 10 micrometers-3 mm.

<Application>
The composition, cured product and laminate of the present invention can be suitably used in the field of structural materials used in the transport industry such as the aircraft industry and the automobile industry, the field of electrical and electronic materials used in the electrical and electronic industry, and the like. . Specifically, for example, sealing materials for electrical and electronic parts, interlayer insulating films, stress relaxation primers; laminated boards (printed wiring boards, interlayer adhesives, solder resists, solder pastes); adhesives (conductive adhesives, Thermal conductive adhesives / adhesive sheets); structural adhesives and prepregs used in various structural materials; various coatings, optical components (optical films such as wave plates and retardation plates, various special products such as conical lenses, spherical lenses, and cylindrical lenses) Lenses, lens arrays, etc.), insulating films for printed wiring boards, and the like. In particular, “Demonstration of
20μm Pitch Micro-vias by Excimer Laser Ablation in Ultra-thin Dry-film Polymer
Dielectrics for Multi-layer RDL on Glass Interposers ”,“ 2015 IEEE Electronic
Components & Technology Conference, 922-927 ”,“ Demonstration of enhanced system-level reliability of ultra-thin BGA packages with circumferential polymer collars and doped solder alloys ”,“ 2016 IEEE 66th Electronic Components and Technology Conference, 1377-1385 ”,“ Modeling, Design, Fabrication and Demonstration of RF Front-End 3D IPAC Module with Ultra-thin Glass Substrates for LTE Applications ”,“ 2016 IEEE 66th Electronic Components and Technology Conference, 1297-1302 ”,“ Design, Demonstration and Characterization of Ultra- thin Low-warpage Glass BGA Packages for Smart Mobile Application Processor ”,“ 2016 IEEE 66th Electronic Components and Technology Conference, 1465-1470 ”,“ Design and Demonstration of Ultra-thin Glass 3D IPD Diplexers ”, 2016 IEEE 66th Electronic Components and Technology It can be suitably used as a material for a mounting structure described in Conference, 2348-2352 ”, etc.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. In the following, “part” and “%” are based on mass unless otherwise specified.

[1] Synthesis of polymer (Synthesis Example 1)
To a four-necked separable flask equipped with a stirrer, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (BisTMC) (18.6 g, 60.0 mmol), 4,6- Dichloropyrimidine (Pym) (8.9 g, 60.0 mmol) and potassium carbonate (11.1 g, 81.0 mmol) were weighed in, N-methyl-2-pyrrolidone (64 g) was added, and 130 ° C. under a nitrogen atmosphere. For 6 hours. After completion of the reaction, N-methyl-2-pyrrolidone (368 g) was added, the salt was removed by filtration, and this solution was poured into methanol (9.1 kg). The precipitated solid was separated by filtration, washed with a small amount of methanol, filtered again and collected, and then dried at 120 ° C. under reduced pressure for 12 hours using a vacuum dryer, and the structure represented by the following formula (P-1) A polymer P-1 having units was obtained (yield; 20.5 g, yield; 90%, weight average molecular weight (Mw); 32,000, glass transition temperature (Tg); 206 ° C.).

(Synthesis Example 2)
To a four-necked separable flask equipped with a stirrer, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (BisTMC) (10.7 g, 34.5 mmol), 3,6- Dichloropyridazine (Pyd) (5.1 g, 34.2 mmol) and potassium carbonate (6.5 g, 47.0 mmol) were weighed in, N-methyl-2-pyrrolidone (36 g) was added, and 145 ° C. under nitrogen atmosphere. For 9 hours. After completion of the reaction, N-methyl-2-pyrrolidone (150 g) was added for dilution, the salt was removed by filtration, and this solution was then poured into methanol (3 kg). The precipitated solid was filtered off, washed with a small amount of methanol, collected again by filtration, dried under the same conditions as in Synthesis Example 1, and polymer P having a structural unit represented by the following formula (P-2) -2 was obtained (yield 7.6 g, yield 48%, weight average molecular weight (Mw); 30,000, glass transition temperature (Tg); 232 ° C.).

(Synthesis Example 3)
To a four-necked separable flask equipped with a stirrer, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (BisTMC) (18.6 g, 60.0 mmol), 4,6- Dichloro-2-phenylpyrimidine (PhPym) (13.7 g, 61.1 mmol) and potassium carbonate (11.4 g, 82.5 mmol) are weighed in, N-methyl-2-pyrrolidone (75 g) is added, and nitrogen atmosphere is added. The reaction was carried out at 130 ° C. for 6 hours. After completion of the reaction, N-methyl-2-pyrrolidone (368 g) was added, the salt was removed by filtration, and this solution was poured into methanol (9.1 kg). The precipitated solid was filtered off, washed with a small amount of methanol, collected again by filtration, dried under the same conditions as in Synthesis Example 1, and polymer P having a structural unit represented by the following formula (P-3) -3 (yield 20.5 g, yield 90%, weight average molecular weight (Mw); 187,000, glass transition temperature (Tg); 223 ° C.).

In addition, the measurement conditions of the weight average molecular weight (Mw) and glass transition temperature (Tg) of each polymer are as follows.
<Weight average molecular weight (Mw)>
The weight average molecular weight (Mw) was measured using a GPC apparatus (“HLC-8320 type” manufactured by Tosoh Corporation) under the following conditions.
Column: Tosoh's “TSKgel α-M” and Tosoh's “TSKgel guardcylum α” linked Developing solvent: N-methyl-2-pyrrolidone Column temperature: 40 ° C.
Flow rate: 1.0 mL / min Sample concentration: 0.75% by mass
Sample injection volume: 50 μL
Detector: Differential refractometer Standard material: Monodisperse polystyrene

<Glass transition temperature (Tg)>
The glass transition temperature (Tg) is measured at a frequency of 1 Hz and a heating rate of 10 ° C./min using a dynamic viscoelasticity measuring device (“DMS7100” manufactured by Seiko Instruments Inc.), and the loss tangent is maximized. It was. The loss tangent was a value obtained by dividing the storage elastic modulus by the loss elastic modulus.

[2] Preparation of composition (Example 1)
10 parts of polymer P-1 and 90 parts of curable compound [liquid epoxy compound (bisphenol A type epoxy, “JER828”, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent; 190 meq / g)] at 130 ° C. for 30 minutes The mixture was stirred with a stirrer. Thereafter, 5 parts of a curing aid [thermosetting agent (1-benzyl-2-methylimidazole, “BMI 12”, manufactured by Mitsubishi Chemical Corporation)] was mixed to prepare a composition.

(Example 2)
Example except that polymer P-1 was changed to 20 parts and curable compound [liquid epoxy compound (bisphenol A type epoxy, “JER828”, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent; 190 meq / g)] A composition was prepared in the same manner as in 1.

(Example 3)
Example except that polymer P-1 was changed to 40 parts and curable compound [liquid epoxy compound (bisphenol A type epoxy, “JER828”, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 190 meq / g)] A composition was prepared in the same manner as in 1.

Example 4
Example except that polymer P-2 was changed to 10 parts and curable compound [liquid epoxy compound (bisphenol A type epoxy, “JER828”, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent; 190 meq / g)] A composition was prepared in the same manner as in 1.

(Example 5)
Example except for changing polymer P-3 to 10 parts and curable compound [liquid epoxy compound (bisphenol A type epoxy, “JER828”, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent; 190 meq / g)] A composition was prepared in the same manner as in 1.

(Example 6)
80 parts of polymer P-1, curable compound [liquid epoxy compound (naphthalene type epoxy, “HP-4032D”, manufactured by DIC, epoxy equivalent; 141 meq / g)], curing aid [thermosetting agent (1-Benzyl-2-methylimidazole, “BMI 12”, manufactured by Mitsubishi Chemical Corporation)] 5 parts and 160 parts of a solvent (cyclopentanone) were mixed to prepare a composition.

(Example 7)
50 parts of polymer P-1 and 50 parts of curable compound [liquid cyanate ester compound (2,2′-bis (4-cyanatophenyl) propane, manufactured by Tokyo Chemical Industry Co., Ltd.)], curing aid [thermosetting 5 parts of an agent (1-benzyl-2-methylimidazole, “BMI 12”, manufactured by Mitsubishi Chemical Corporation)] and 160 parts of a solvent (cyclopentanone) were mixed to prepare a composition.

(Comparative Example 1)
10 parts of polyphenylene ether (PPE) (glass transition temperature (Tg); 215 ° C.) and curable compound [liquid epoxy compound (bisphenol A type epoxy, “JER828”, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 190 meq / g) 90 parts were stirred with a stirrer at 130 ° C. for 30 minutes. Thereafter, 5 parts of a curing aid [thermosetting agent (1-benzyl-2-methylimidazole, “BMI 12”, manufactured by Mitsubishi Chemical Corporation)] was mixed to prepare a composition.

(Comparative Example 2)
100 parts of curable compound [liquid epoxy compound (bisphenol A type epoxy, “JER828”, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent; 190 meq / g)], and curing aid [thermosetting agent (1-benzyl-2-methyl Imidazole, “BMI 12”, manufactured by Mitsubishi Chemical Corporation)] was mixed to prepare a composition.

(Comparative Example 3)
The composition prepared in Comparative Example 2 was further mixed with 160 parts of a solvent (cyclopentanone) to prepare a composition.

(Comparative Example 4)
Curing compound [liquid cyanate ester compound (2,2′-bis (4-cyanatophenyl) propane, manufactured by Tokyo Chemical Industry Co., Ltd.)], curing aid [thermosetting agent (1-benzyl-2-methyl Imidazole, “BMI 12”, manufactured by Mitsubishi Chemical Corporation)] and 160 parts of a solvent (cyclopentanone) were mixed to prepare a composition.

(Comparative Example 5)
A composition was prepared by mixing 100 parts of the polymer P-1 and 160 parts of a solvent (cyclopentanone).

[3] Evaluation of composition and cured product obtained using the composition and results thereof (3-1) Characteristics of composition (solubility, solubility change)
<Solubility>
About each composition of Examples 1-5 and Comparative Examples 1-2, the weight to a curable compound at the time of preparing the polymer and a liquid curable compound at 130 degreeC for 30 minutes at the time of preparation of each composition was carried out. The solubility of the coalesced was visually evaluated. At this time, no agglomerates were confirmed, and “◯” was given when the solution was a homogeneous solution, “Δ” when the agglomerate remained, and “x” when it was not dissolved at all. The results are shown in Table 1.

<Solubility change>
About each composition of Examples 6-7 and Comparative Examples 3-5, the change of the solubility to the organic solvent before and behind hardening was evaluated as follows.
(Solubility before curing)
1 part of each composition was mixed with 100 parts of an organic solvent [N-methyl-2-pyrrolidone (NMP)], and the solubility in NMP was evaluated. At this time, when no aggregate was confirmed and the solution was a homogeneous solution, it was defined as “dissolved”, and when the aggregate remained, it was determined as “insoluble”.
(Solubility after curing)
Each composition was applied onto a release film by a bar coater and heated at 70 ° C. for 15 minutes. Subsequently, after heating at 120 degreeC for 15 minutes, the cured | curing material for evaluation (2 cm x 3 cm x 50 micrometers in thickness) was created by further heating at 180 degreeC for 2 hours. Thereafter, the obtained cured product was immersed in NMP (50 ml) at room temperature for 24 hours and then dried. Then, the residual rate (%) is calculated by the formula [(weight of cured product after immersion drying) / (weight of cured product before immersion) × 100], and the case where this value is 90% or more is defined as “insoluble”. The case of less than 90% was defined as “dissolution”.
(Evaluation criteria)
A case where the solubility of the composition before curing in NMP was “dissolution” and the solubility of the cured product in NMP was “insoluble” was designated as “◯”. On the other hand, the case where the solubility of the composition before curing in NMP was “dissolution” and the solubility of the cured product in NMP was “dissolution” was designated as “x”. The results are shown in Table 2.

(3-2) Properties of cured product [chemical resistance, toughness (tensile strength, tensile elongation, shear strength), heat resistance (glass transition temperature)]
About the hardened | cured material obtained using each composition of Examples 1-7 and Comparative Examples 1-5, each characteristic was evaluated or analyzed as follows.
<Chemical resistance>
Each composition was sandwiched between mold-released wafers and heated at 180 ° C. for 2 hours to prepare a cured product for evaluation (2 cm × 3 cm × thickness 50 μm). Thereafter, the obtained cured product was immersed in 50 ml of N-methyl-2-pyrrolidone (NMP) at room temperature for 24 hours and then dried. Then, the residual rate (%) is calculated by the formula [(weight of cured product after immersion drying) / (weight of cured product before immersion) × 100]. , Less than 90% was taken as "x". The results are shown in Tables 1 and 2.

<Tensile strength and tensile elongation>
Each composition was sandwiched between mold-released wafers and heated at 180 ° C. for 2 hours to prepare a cured product for evaluation (5 mm × 1 cm × 50 μm thickness). Thereafter, the obtained cured product was pulled at 5 mm / min using “Instron 5567” manufactured by Instron, and the maximum stress when it was ruptured was defined as the tensile strength and the maximum elongation as the tensile elongation. The results are shown in Tables 1 and 2.

<Shear strength>
Each composition was sandwiched between aluminum plates (25 mm × 100 mm × thickness 2 mm) anodized with phosphoric acid and heated at 180 ° C. for 2 hours to prepare a test piece for evaluating shear strength. In accordance with JIS K6850, the created test piece was “Instron 5567” manufactured by Instron Corporation, and the maximum load when the test piece was pulled at a tensile speed of 1 mm / min was defined as shear strength. The results are shown in Tables 1 and 2. In Examples 1 to 5 and Comparative Examples 1 and 2, the curing aid in the resin composition was changed from 5 parts of 1-benzyl-2-methylimidazole to dicyandiamide [thermosetting agent, “DICY 7” (50% (Particulate product with a particle size of 3 μm), manufactured by Mitsubishi Chemical Co., Ltd.].

<Glass transition temperature>
Each composition was sandwiched between mold-released wafers and heated at 180 ° C. for 2 hours to prepare a cured product for evaluation (3 mm × 1 cm × thickness 50 μm). Thereafter, the obtained cured product was measured with a DMS tester (model number “EXSTAR4000”, manufactured by Seiko Instruments Inc.) within a temperature range of 23 ° C. to 350 ° C. under a measurement condition of 1 Hz, and Tan δ was a glass transition. It was temperature. The results are shown in Tables 1 and 2.

(3-3) Evaluation Results According to the solubility evaluation results in Table 1, the [A] polymer (polymers (P-1) to (P-3) obtained in [1] above) was carried out. The composition of Examples 1-5 was a uniform solution, and evaluation was "(circle)". On the other hand, instead of the [A] polymer, the composition of Comparative Example 1 containing a known resin (polyphenylene ether) was not a homogeneous solution, and aggregates remained, and the evaluation was “Δ”. From this, the [A] polymer contained in Examples 1-5 is excellent in the solubility to thermosetting compounds, such as an epoxy compound, compared with known resin (polyphenylene ether). It could be confirmed. Moreover, since the composition of Examples 1-5 is excellent in the solubility to a curable compound as mentioned above, it can be utilized as a non-solvent type composition.

Moreover, according to the evaluation result of the solubility change in Table 2, the cured product of Comparative Example 5 containing [A] polymer (P-1) and no curable compound includes N-methylpyrrolidone. It was dissolved in a solvent, and the evaluation was “x”. On the other hand, each hardened | cured material of Examples 6-7 containing a polymer (P-1) and a sclerosing | hardenable compound (an epoxy compound or a cyanate ester compound) is a solvent including N-methylpyrrolidone. The evaluation was “◯”. From this, it was confirmed that the solubility of the composition after curing was changed and the chemical resistance was improved by blending the thermosetting compound.

  Furthermore, according to the evaluation results of tensile strength, tensile elongation and shear strength in Tables 1 and 2, the cured products of Examples 1 to 7 including the polymer [A] include a known resin (polyphenylene ether). It was confirmed that the strength was improved as compared with the cured product of Comparative Example 1. Furthermore, according to the result of the glass transition degree of hardened | cured material, it can confirm that heat resistance is improved with the hardened | cured material of the composition of Examples 1-7 rather than the hardened | cured material of the composition of the comparative example 1. It was.

  According to the resin composition of this invention, the laminated body provided with the hardened | cured material excellent in the performance balance of toughness, heat resistance, and chemical resistance, and its hardened | cured material layer can be obtained. In particular, a cured product that has both excellent toughness and excellent heat resistance and excellent chemical resistance, and a laminate including the cured product layer can be obtained. Therefore, the present invention can be suitably used in a wide range of fields such as the transportation industry (for example, the aircraft industry, the automobile industry, etc.) and the electrical and electronics industry.

Claims (5)

It contains a polymer having a structural unit represented by at least one of the following formulas (1-1), (1-2) and (1-3), and a curable compound. Composition.

[In formulas (1-1) to (1-3), each R ¹ independently represents a halogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent halogen having 1 to 20 carbon atoms. Or a salt of a primary hydrocarbon group, a nitro group, a cyano group, a primary to tertiary amino group, or a primary to tertiary amino group. n is an integer of 0-2 each independently. When n is 2, the plurality of R ¹ may be the same or different, and may be bonded in any combination to form part of the ring structure. ]   The composition according to claim 1, wherein the curable compound is at least one of an epoxy compound, a cyanate ester compound, a vinyl compound, a silicone compound, an oxazine compound, a maleimide compound, and an allyl compound.   The composition according to claim 1 or 2, further comprising a curing aid.   Hardened | cured material formed by hardening | curing the composition in any one of Claims 1 thru | or 3.   A laminate comprising: a substrate; and a cured resin layer formed using the composition according to claim 1 on the substrate.