JP2005290061A - Polymer composition and crosslinked polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a crosslinked polymer showing in particular excellent heat resistance even at 350°C or higher without deteriorating mechanical strength, moisture resistance, electrical characteristics and other characteristics, and to provide a polymer composition which gives the above crosslinked polymer. <P>SOLUTION: The polymer composition contains a compound having an amino group and a compound having an active ester group, wherein at least either of the amino group-bearing compound and the active ester group-bearing compound is a polymer. The above active ester group is represented by general formula (1), wherein R is an alkyl group, pyridyl group, quinolyl group, aromatic group or benzotriazole group, and the hydrogen atoms in these groups may be substituted by at least one organic group. The crosslinked polymer is obtainable by crosslinking the polymer chains by making the above polymer composition to react. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a polymer composition and a crosslinked polymer.

  Thermosetting resins typified by phenol resins are excellent in heat resistance, mechanical strength, moisture resistance, and the like, and are widely used in various fields such as electronic materials, automotive members, and adhesives. However, the present condition is that the material which satisfy | fills all the requirements in the advanced field | areas by which severer heat resistance is requested | required especially especially the electronic material field | area has not been obtained yet.

  In particular, in advanced fields where high thermal stability of 350 ° C. or higher is required, if the thermal decomposition start temperature of the resin is lower than 350 ° C., the dimensional stability during heating will be adversely affected, or in a high temperature environment, The generated pyrolysis gas may adversely affect not only the quality of products using these resins but also the production apparatus.

As an improvement measure, we focused on thermally crosslinkable carbon-carbon triple bonds, and by introducing alkynes into the resin, the heat-cured resin structure was made into a three-dimensional network, and heat resistance was improved. Techniques relating to curable resins are disclosed. Examples thereof include a technique related to a thermosetting resin in which propargyl ether groups are introduced into a phenol resin at a high density (for example, see Patent Document 1), and a technique related to a thermosetting resin in which an ethynyl group is introduced into polyphenol (for example, a patent). Document 2, Patent Document 3, and Non-Patent Document 1). However, even with these thermosetting resins, the heat resistance is not sufficient.
JP-T-1-503541 (Pages 1-3 and 8) JP-A-9-107984 JP 2000-63499 A Tonami, H .; Kobayashi, S .; Fujita, T .; Taguchi, Y; Osada, K; Biomacromolecules, 2000, 1 (2), 149-151.

  The problem to be solved was made to solve the above-mentioned problems, and the object is to reduce the mechanical strength, moisture resistance, electrical characteristics and other characteristics, particularly at 350 ° C. The object of the present invention is to provide a crosslinked polymer exhibiting excellent heat resistance and a polymer composition from which the crosslinked polymer is obtained.

  The present invention is obtained as a novel thermosetting resin excellent in heat resistance, obtained by crosslinking a polymer chain from a polymer composition containing a compound having an amino group and a compound having an active ester group. The most main feature is to provide a crosslinked polymer.

That is, the present invention
1. A polymer composition comprising a compound having an amino group and a compound having an active ester group, wherein at least one of the compound having an amino group and the compound having an active ester group is a polymer. A polymer composition,
2. The polymer composition according to Item 1, wherein the active ester group is represented by the following general formula (1):

（式（１）中、Ｒはアルキル基、ピリジル基、キノリル基、芳香族基、又はベンゾトリアゾール基を示し、これらの基における水素原子は、少なくとも１個の有機基で置換されていても良い。）

(In the formula (1), R represents an alkyl group, a pyridyl group, a quinolyl group, an aromatic group, or a benzotriazole group, and a hydrogen atom in these groups may be substituted with at least one organic group. .)

3. The polymer composition according to item 1 or 2, wherein the compound having an amino group has a repeating unit represented by the following general formula (2):

（式中のＡｒは、芳香族基を示す。Ｘは、脂肪族基、芳香族基、スルホニル基および酸素原子の中から選ばれる少なくとも１種の基で構成される基を示す。式中のｍは、２以上、１００００以下の整数を示す。式中のｎは、１以上、３以下の整数を示す。）

(Ar in the formula represents an aromatic group. X represents a group composed of at least one group selected from an aliphatic group, an aromatic group, a sulfonyl group and an oxygen atom. m represents an integer of 2 or more and 10,000 or less, and n in the formula represents an integer of 1 or more and 3 or less.

4). The polymer composition according to any one of Items 1 to 3, wherein the compound having an amino group is represented by the following general formula (3):

（式中のＡｒは、芳香族基を示す。式中のａは、１以上、６以下の整数を示す。）

(Ar in the formula represents an aromatic group. In the formula, a represents an integer of 1 or more and 6 or less.)

5). The polymer composition according to any one of Items 2 to 4, wherein the compound having an active ester group has a repeating unit represented by the following general formula (4):

［式（４）中、−ＣＯＯＲは、同一のベンゼン環上に１〜５個を有していても良い。Ａｒは、芳香族基を示す。Ｘは、脂肪族基、芳香族基、スルホニル基および酸素原子の中から選ばれる少なくとも１種の基で構成される基を示す。式中のｍは、２以上、１００００以下の整数を示す。式中のｎは、１以上、３以下の整数を示す。］

[In Formula (4), -COOR may have 1 to 5 on the same benzene ring. Ar represents an aromatic group. X represents a group composed of at least one group selected from an aliphatic group, an aromatic group, a sulfonyl group, and an oxygen atom. M in the formula represents an integer of 2 or more and 10,000 or less. N in the formula represents an integer of 1 or more and 3 or less. ]

6). The polymer composition according to any one of Items 2 to 5, wherein the compound having an active ester group is represented by the following general formula (5):

（式中のＡｒは、芳香族基を示す。式中のａは、１以上、６以下の整数を示す。）

(Ar in the formula represents an aromatic group. In the formula, a represents an integer of 1 or more and 6 or less.)

7). The polymer composition according to any one of Items 1 to 6, wherein the compound having an active ester group is a benzoxazole resin precursor,
8). The polymer composition according to any one of items 1 to 7, comprising an organic solvent capable of dissolving or dispersing the polymer composition,
9. A crosslinked polymer obtainable by crosslinking the polymer chain by reacting the polymer composition according to any one of items 1 to 8;
Is to provide.

  ADVANTAGE OF THE INVENTION According to this invention, the thermal stability at the time of a heating improves dramatically, The crosslinked polymer which shows the outstanding heat resistance also in the high temperature range of 350 degreeC or more can be provided.

  The crosslinked polymer of the present invention comprises a compound having an amino group and a compound having an active ester group, at least one of which is a polymer, that is, a compound having a polymer amino group and an active ester group that is not a polymer. A combination of a compound having a non-polymer amino group and a compound having a polymer active ester group, a combination of a compound having a polymer amino group and a compound having a polymer active ester group, Alternatively, these mixtures can be obtained by making the resin structure three-dimensional by a cross-linking reaction between polymer chains by reacting them with heating, and reacting an amino group with an active ester group. Therefore, it is possible to crosslink at a temperature lower than that of the carbon-carbon triple bond, and to improve the heat resistance of the polymer after crosslinking. It can be.

  Examples of the compound having a polymeric amino group used in the present invention include those having a repeating unit represented by the general formula (2). Examples of the compound having a non-polymeric amino group include those represented by the general formula (3). And those having a repeating unit represented by:

  In the present invention, examples of the aromatic group represented by Ar in the general formula (2) include a phenylene group, a naphthalenediyl group, a binaphthyldiyl group, an anthracenediyl group, a phenanthrenediyl group, a biphenyldiyl group, and a biphenylenediyl group. , Fluorenediyl group, biphenyl fluorenediyl group, pyridinediyl group, and the like, but are not limited thereto. The hydrogen atom in these groups may be substituted with an aliphatic group, an aromatic group and a fluorine atom. Examples of the aliphatic group include alkyl groups having 1 to 20 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group: carbons such as a methoxy group, an ethoxy group, a propyloxy group, and a butoxy group. Alkoxy group having 1 or more and 20 or less: Alkenyl group having 1 or more and 20 or less carbon atoms such as vinyl group, propenyl group and butenyl group: Carbon number such as ethynyl group, propynyl group and butynyl group is 1 or more 20 or less alkynyl groups: cyclopentyl group, cyclohexyl group, adamantyl group, diamantyl group and biadamantyl group and the like, and the like. Examples of the aromatic group include a phenyl group, Examples thereof include, but are not limited to, naphthyl group, phenoxy group, and naphthoxy group. Moreover, the hydrogen atom in the said aliphatic group and aromatic group may be substituted by the fluorine atom.

  In the present invention, the group represented by X in the general formula (2) is a group composed of at least one group selected from an aliphatic group, an aromatic group, a sulfonyl group, and an oxygen atom. The aliphatic group has 1 to 20 carbon atoms, such as a methylene group, ethylene group, propylene group, and butylene group, and 1 to 20 carbon atoms, such as an alkylene group, vinylene group, propenylene group, and butenylene group. The following alkenylene group, ethynylene group, propynylene group, butynylene group and the like are exemplified by alkynylene groups having 1 to 20 carbon atoms, and examples of the aromatic group include phenylene group, naphthalenediyl group, and biphenyldiyl. Group, fluorenediyl group, biphenyl fluorenediyl group and pyridinediyl group. Not intended to be. The hydrogen atom in these groups may be substituted with an aliphatic group, an aromatic group and a fluorine atom. Examples of the aliphatic group include alkyl groups having 1 to 20 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group: carbons such as a methoxy group, an ethoxy group, a propyloxy group, and a butoxy group. Alkoxy group having 1 or more and 20 or less: Alkenyl group having 1 or more and 20 or less carbon atoms such as vinyl group, propenyl group and butenyl group: Carbon number such as ethynyl group, propynyl group and butynyl group is 1 or more 20 or less alkynyl groups: cyclopentyl group, cyclohexyl group, adamantyl group, diamantyl group and biadamantyl group and the like, and the like. Examples of the aromatic group include a phenyl group, Examples thereof include, but are not limited to, naphthyl group, phenoxy group, and naphthoxy group. Moreover, the hydrogen atom in the said aliphatic group and aromatic group may be substituted by the fluorine atom.

  Examples of the compound having the structure represented by the general formula (2) include poly ((4-amino-3-hydroxyphenoxy) phenylenemethylene) and poly ((4-amino-3-hydroxyphenoxy) phenylene-phenyl. Methylene), poly ((4-amino-3-hydroxyphenoxy) phenylene-adamantylmethylene), poly (4-adamantyl-1- (4-amino-3-hydroxyphenoxy) phenylenemethylene), poly (4-adamantyl-1) -(4-amino-3-hydroxyphenoxy) phenylene-phenylmethylene), poly (4-adamantyl-1- (4-amino-3-hydroxyphenoxy) phenylene-adamantylmethylene), poly (bis (4-amino-3) -Hydroxyphenoxy) phenylenemethylene), poly (bis 4-amino-3-hydroxyphenoxy) phenylene-phenylmethylene), poly (bis (4-amino-3-hydroxyphenoxy) phenylene-adamantylmethylene), poly (bis (4-amino-3-hydroxyphenoxy) biphenyldiylmethylene) ), Poly ((4-amino-3-hydroxyphenoxy) naphthalenediylmethylene), poly ((4-amino-3-hydroxyphenoxy) naphthalenediyl-phenylmethylene), poly ((4-amino-3-hydroxyphenoxy) Naphthalenediyl-adamantylmethylene), poly ((4-amino-3-hydroxyphenoxy) fluorangeylmethylene), poly ((4-amino-3-hydroxyphenoxy) fluorangeyl-phenylmethylene), poly ((4- Amino-3-hi Roxyphenoxy) fluorangeyl-adamantylmethylene), poly (bis ((4-amino-3-hydroxyphenoxy) phenyl) fluoylylmethylene), poly (bis ((4-amino-3-hydroxyphenoxy) phenyl) fur Compounds having a poly (arylene methylene) structure such as orangeyl-phenylmethylene) and poly (bis ((4-amino-3-hydroxyphenoxy) phenyl) fluorangeyl-adamantylmethylene), poly ((4-amino -3-hydroxyphenoxy) phenylene vinylene), poly (bis (4-amino-3-hydroxyphenoxy) phenylene vinylene), poly (bis (4-amino-3-hydroxyphenoxy) biphenyldiylvinylene), poly ((4- Amino-3-hydroxyph Poly ((enoxy) naphthalenediylvinylene), poly ((4-amino-3-hydroxyphenoxy) fluorangeylvinylene) and poly (bis ((4-amino-3-hydroxyphenoxy) phenyl) fluorangeylvinylene)), etc. Compound having (arylene vinylene) structure: poly ((4-amino-3-hydroxyphenoxy) phenylene ethynylene), poly (bis (4-amino-3-hydroxyphenoxy) phenylene ethynylene), poly (bis (4 -Amino-3-hydroxyphenoxy) biphenyldiylethynylene), poly ((4-amino-3-hydroxyphenoxy) naphthalenediylethynylene), poly ((4-amino-3-hydroxyphenoxy) fluorangeylethynylene) And poly (bis ((4-amino- Compounds having a poly (arylene ethynylene) structure, such as:-(hydroxyphenoxy) phenyl) fluorangeylethynylene), poly ((4-amino-3-hydroxyphenoxy) phenylene ether), poly (bis (4-amino) -3-hydroxyphenoxy) phenylene ether), poly (bis (4-amino-3-hydroxyphenoxy) biphenyldiyl ether), poly ((4-amino-3-hydroxyphenoxy) naphthalenediyl ether), poly ((4- Compounds having a poly (arylene ether) structure such as amino-3-hydroxyphenoxy) fluorenediyl ether) and poly (bis ((4-amino-3-hydroxyphenoxy) phenyl) fluorenediyl ether), poly ( (4-amino-3-hydro Ciphenoxy) phenylenesulfonyl), poly (bis (4-amino-3-hydroxyphenoxy) phenylenesulfonyl), poly (bis (4-amino-3-hydroxyphenoxy) biphenyldiylsulfonyl), poly ((4-amino-3 -Hydroxyphenoxy) naphthalenediylsulfonyl), poly ((4-amino-3-hydroxyphenoxy) fluorenediylsulfonyl) and poly (bis ((4-amino-3-hydroxyphenoxy) phenyl) fluorenediylsulfonyl), etc. Compounds having a poly (arylenesulfonyl) structure: poly ((4-amino-3-hydroxyphenoxy) phenylene), poly ((4-amino-3-hydroxyphenoxy) phenylenephenylene), poly (bis (4-amino) -3-hydroxyph Enoxy) phenylene), poly (bis (4-amino-3-hydroxyphenoxy) biphenyldiyl), poly ((4-amino-3-hydroxyphenoxy) naphthalenediyl), poly ((4-amino-3-hydroxyphenoxy) Compounds having a poly (arylene) structure such as fluorenediyl) and poly (bis ((4-amino-3-hydroxyphenoxy) phenyl) fluorenediyl), but are not limited thereto. It is not something.

  Examples of the compound having an amino group represented by the general formula (3) include compounds having dihydroxylbenzene such as 2,4-diamino-resorcinol and 2,5-diamino-1,4-dihydroxylbenzene: Compounds having dihydroxy-biphenyl such as 3,3′-diamino-4,4′-dihydroxy-biphenyl and 3,3′-dihydroxy-4,4′-diamino-biphenyl: 3,3′-diamino-4 Bisaminophenol compounds having dihydroxy-diphenyl ether such as 4,4'-dihydroxy-diphenyl ether: 9,9-bis (3-amino-4-hydroxy-phenyl) fluorene and 9,9-bis (4- (4-amino Having a fluorene skeleton such as -3-hydroxy) -phenoxy-phenyl) fluorene Compound: Compound having binaphthalene skeleton such as 2,2′-bis- (4-amino-3-hydroxy-phenoxy) -1,1′-binaphthalene: 3,3′-diamino-4,4′-dihydroxy Compounds having a sulfone group such as -diphenylsulfone, bis (4- (4-amino-3-hydroxy) -phenoxy-phenyl) sulfone and bis (4- (4-hydroxy-3-amino) phenoxy-phenyl) sulfone: And compounds having fluorine or a fluorinated alkyl group such as 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, but are not limited thereto.

  The compound having an active ester group used in the present invention is preferably a compound having a group represented by the general formula (1), and the compound having a polymer active ester group is represented by the general formula (4). Examples of the compound having an active ester group that is not a polymer include the compound represented by the general formula (5).

  In the present invention, examples of R of the active ester group represented by the general formula (1) include a hydrogen atom, an alkyl group, a pyridyl group, a quinolyl group, an aromatic group, or a benzotriazole group. Specifically, alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, isobutyl group and sec-butyl group: 2-pyridyl group, 3-pyridyl group Groups and pyridyl groups such as 4-pyridyl group: quinolyl groups such as 2-quinolyl group, 3-quinolyl group, 4-quinolyl group, 5-quinolyl group, 6-quinolyl group, 7-quinolyl group and 8-quinolyl group : Aromatic groups such as phenyl group, 1-naphthyl group and 2-naphthyl group: Benzotriazole groups such as 1-benzotriazole group: and the like, but are not limited thereto.

  In the present invention, examples of the aromatic group represented by Ar in the general formula (4) include a phenylene group, a naphthalenediyl group, a binaphthyldiyl group, an anthracenediyl group, a phenanthrenediyl group, a biphenyldiyl group, and a biphenylenediyl group. Groups, fluorenediyl groups, biphenyl fluorenediyl groups, pyridinediyl groups, and the like, but are not limited thereto. The hydrogen atom in these groups may be substituted with an aliphatic group, an aromatic group and a fluorine atom. Examples of the aliphatic group include alkyl groups having 1 to 20 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group: carbons such as a methoxy group, an ethoxy group, a propyloxy group, and a butoxy group. Alkoxy group having 1 or more and 20 or less: Alkenyl group having 1 or more and 20 or less carbon atoms such as vinyl group, propenyl group and butenyl group: Carbon number such as ethynyl group, propynyl group and butynyl group is 1 or more 20 or less alkynyl groups: cyclopentyl group, cyclohexyl group, adamantyl group, diamantyl group and biadamantyl group and the like, and the like. Examples of the aromatic group include a phenyl group, Examples thereof include, but are not limited to, naphthyl group, phenoxy group, and naphthoxy group. Moreover, the hydrogen atom in the said aliphatic group and aromatic group may be substituted by the fluorine atom.

  In the present invention, the group represented by X in the general formula (4) is a group composed of at least one group selected from an aliphatic group, an aromatic group, a sulfonyl group, and an oxygen atom. And, as the aliphatic group, for example, an alkylene group having 1 to 20 carbon atoms such as a methylene group, an ethylene group, a propylene group, and a butylene group, and a carbon number such as an alkylene group, a vinylene group, a propenylene group, and a butenylene group. Examples of the aromatic group include, for example, a phenylene group and a naphthalenediyl group. Examples of the aromatic group include 20 or less alkenylene group, ethynylene group, propynylene group, and butynylene group. , Biphenyldiyl group, fluorenediyl group, biphenyl fluorenediyl group and pyridinediyl group, etc. But it is not limited thereto. The hydrogen atom in these groups may be substituted with an aliphatic group, an aromatic group and a fluorine atom. Examples of the aliphatic group include alkyl groups having 1 to 20 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group: carbons such as a methoxy group, an ethoxy group, a propyloxy group, and a butoxy group. Alkoxy group having 1 or more and 20 or less: Alkenyl group having 1 or more and 20 or less carbon atoms such as vinyl group, propenyl group and butenyl group: Carbon number such as ethynyl group, propynyl group and butynyl group is 1 or more 20 or less alkynyl groups: cyclopentyl group, cyclohexyl group, adamantyl group, diamantyl group and biadamantyl group and the like, and the like. Examples of the aromatic group include a phenyl group, Examples thereof include, but are not limited to, naphthyl group, phenoxy group, and naphthoxy group. Moreover, the hydrogen atom in the said aliphatic group and aromatic group may be substituted by the fluorine atom.

  Examples of the compound having the structure represented by the general formula (4) include poly ((4-carboxyphenoxy) phenylenemethylene), poly ((4-carboxyphenoxy) phenylene-phenylmethylene), poly ((4- Carboxyphenoxy) phenylene-adamantylmethylene), poly (4-adamantyl-1- (4-carboxyphenoxy) phenylenemethylene), poly (4-adamantyl-1- (4-carboxyphenoxy) phenylene-phenylmethylene), poly (4 -Adamantyl-1- (4-carboxyphenoxy) phenylene-adamantylmethylene), poly (bis (4-carboxyphenoxy) phenylenemethylene), poly (bis (4-carboxyphenoxy) phenylene-phenylmethylene), poly (bis (4 -Carboki Phenoxy) phenylene-adamantylmethylene), poly (bis (4-carboxyphenoxy) biphenyldiylmethylene), poly ((4-carboxyphenoxy) naphthalenediylmethylene), poly ((4-carboxyphenoxy) naphthalenediyl-phenylmethylene), Poly ((4-carboxyphenoxy) naphthalenediyl-adamantylmethylene), poly ((4-carboxyphenoxy) fluorangeylmethylene), poly ((4-carboxyphenoxy) fluorangeyl-phenylmethylene), poly ((4- Carboxyphenoxy) fluorangeyl-adamantylmethylene), poly (bis ((4-carboxyphenoxy) phenyl) fluoylylmethylene), poly (bis ((4-carboxyphenoxy) phenyl) fur Compounds having a poly (arylene methylene) structure, such as orangeyl-phenylmethylene) and poly (bis ((4-carboxyphenoxy) phenyl) fluorangeyl-adamantylmethylene), poly ((4-carboxyphenoxy) phenylene vinylene ), Poly (bis (4-carboxyphenoxy) phenylene vinylene), poly (bis (4-carboxyphenoxy) biphenyldiylvinylene), poly ((4-carboxyphenoxy) naphthalenediylvinylene), poly ((4-carboxyphenoxy) Compounds having a poly (arylene vinylene) structure, such as fluorangeylvinylene) and poly (bis ((4-carboxyphenoxy) phenyl) fluorangeylvinylene), poly ((4-carboxyphenoxy) pheny Lenethynylene), poly (bis (4-carboxyphenoxy) phenyleneethynylene), poly (bis (4-carboxyphenoxy) biphenyldiylethynylene), poly ((4-carboxyphenoxy) naphthalenediylethynylene), poly ((4 Compounds having a poly (arylene ethynylene) structure, such as -carboxy (phenoxy) fluorangeylethynylene) and poly (bis ((4-carboxyphenoxy) phenyl) fluorangeylethynylene): poly ((4-carboxy Phenoxy) phenylene ether), poly (bis (4-carboxyphenoxy) phenylene ether), poly (bis (4-carboxyphenoxy) biphenyldiyl ether), poly ((4-carboxyphenoxy) naphthalenediyl ether), poly ( Compounds having a poly (arylene ether) structure such as 4-carboxyphenoxy) fluorenediyl ether) and poly (bis ((4-carboxyphenoxy) phenyl) fluorenediyl ether), poly ((4-carboxyphenoxy) Phenylenesulfonyl), poly (bis (4-carboxyphenoxy) phenylenesulfonyl), poly (bis (4-carboxyphenoxy) biphenyldiylsulfonyl), poly ((4-carboxyphenoxy) naphthalenediylsulfonyl), poly ((4-carboxy Compounds having a poly (arylenesulfonyl) structure such as phenoxy) fluorangeylsulfonyl) and poly (bis ((4-carboxyphenoxy) phenyl) fluorangeylsulfonyl), poly ((4-carbo Ciphenoxy) phenylene), poly ((4-carboxyphenoxy) phenylenephenylene), poly (bis (4-carboxyphenoxy) phenylene), poly (bis (4-carboxyphenoxy) biphenyldiyl), poly ((4-carboxyphenoxy) ) Naphthalenediyl), poly ((4-carboxyphenoxy) fluorenediyl) and poly (bis ((4-carboxyphenoxy) phenyl) fluorenediyl), etc., compounds having a poly (arylene) structure: However, it is not limited to these.

  Examples of the compound represented by the general formula (5) include phthalic acids such as isophthalic acid, terephthalic acid, 2-fluoroisophthalic acid and 2,3,5,6-tetrafluoroterephthalic acid: 4,4 ′ -Biphenyldicarboxylic acid, 3,4'-biphenyldicarboxylic acid, 3,3'-biphenyldicarboxylic acid, 4,4'-bis (4-carboxyphenoxy) biphenyl and 4,4'-bis (3-carboxyphenoxy) biphenyl Biphenyl dicarboxylic acids such as: 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid and 2,6-naphthalenedicarboxylic acid, etc .: 4,4′-sulfonylbisbenzoic acid, 3,4 '-Sulfonylbisbenzoic acid, 3,3'-sulfonylbisbenzoic acid, 4,4'-oxybisbenzoic acid Bisbenzoic acids such as 3,4′-oxybisbenzoic acid and 3,3′-oxybisbenzoic acid: 2,2-bis (4-carboxyphenyl) propane, 2,2-bis (3-carboxyphenyl) propane, Bis-carboxyphenyl-propane (hexafluoropropane) such as 2,2-bis (4-carboxyphenyl) hexafluoropropane and 2,2-bis (3-carboxyphenyl) hexafluoropropane: 9,9-bis ( 4- (4-Carboxyphenoxy) phenyl) fluorene, 9,9-bis (4- (3-carboxyphenoxy) phenyl) fluorene, 9,9-bis- (2-carboxy-phenyl) fluorene and 9,9-bis -Dicarboxylic acid having a fluorene skeleton such as (3-carboxy-phenyl) fluorene: 4,4'- S- (4-carboxyphenoxy) -p-terphenyl and 4,4′-bis (4-carboxyphenoxy) -m-terphenyl and the like bis-carboxyphenyl-terphenyl: Although the compound converted into the ester group can be mentioned, it is not limited to these.

  In this invention, the benzoxazole resin precursor which has an active ester group can mention the benzoxazole resin precursor which has a repeating unit represented by following General formula (6), for example. The benzoxazole resin precursor is preferable because it has excellent heat resistance after dehydration and ring closure.

［式（６）中、Ｙ₁は有機基を示し、Ｘ₂は式（７）で表される基の中から選ばれる少なくとも１種の基を示し、ｌは２〜１，０００の間の整数である。］

［式（７）中、Ｚは、前記式（１）で表される活性エステル基を示す。また、Ｚは、同一のベンゼン環上に１〜４個を有していても良い。式（７）で表される基における、ベンゼン環上の水素原子は、アルキル基、芳香族基、エーテル基、水酸基、およびフッ素原子の中から選ばれる、少なくとも１個の基で置換されていても良い。］

[In formula (6), Y ₁ represents an organic group, X ₂ represents at least one group selected from the groups represented by formula (7), and l is between 2 and 1,000. It is an integer. ]

[In Formula (7), Z shows the active ester group represented by the said Formula (1). Z may have 1 to 4 on the same benzene ring. The hydrogen atom on the benzene ring in the group represented by the formula (7) is substituted with at least one group selected from an alkyl group, an aromatic group, an ether group, a hydroxyl group, and a fluorine atom. Also good. ]

Examples of the organic group represented by Y ₁ in the repeating unit represented by the formula (6) include a phenyl group, a biphenyl group, a naphthyl group, a diphenylsulfone group, a diphenyl ether group, a fluorenyl group, a phenylfluorenyl group, and biphenylene. Groups and the like.

  The number of repeating units (l) of the repeating unit represented by the formula (6) is not particularly limited, but is preferably an integer of 2 to 1,000, particularly preferably an integer of 5 to 600, and most preferably 10 to 80 Integers up to are preferred. When the number of repeating units is within the above range, the workability when the benzoxazole resin precursor is dissolved in a solvent is excellent.

  Moreover, in this invention, the benzoxazole resin precursor which has an active ester group can mention the benzoxazole resin precursor which has a repeating unit represented by following General formula (8), for example. The benzoxazole resin precursor is preferable because it has excellent heat resistance after dehydration and ring closure.

［式（８）中、Ｒ₁およびＲ₂はそれぞれ独立に水素原子または有機基を示し、Ｘ₁は有機基を示し、Ｙ₂は式（７）で表される基の中から選ばれる少なくとも１種の基を示し、ｍは２〜１，０００の間の整数である。］

[In Formula (8), R ₁ and R ₂ each independently represent a hydrogen atom or an organic group, X ₁ represents an organic group, and Y ₂ is at least selected from the groups represented by Formula (7). 1 type is shown, m is an integer between 2-1,000. ]

Examples of the organic group represented by R ₁ and R ₂ in the repeating unit represented by the formula (8) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and t-butyl. And alkyl groups such as an isobutyl group and a sec-butyl group.

Examples of the organic group represented by X ₁ in the repeating unit represented by the formula (8) include a phenyl group, a biphenyl group, a diphenyl ether group, a fluorenyl group, a binaphthalene group, a sulfide biphenyl group, a binaphthalene group, and a naphthol group. Can be mentioned.

  The number of repeating units (m) of the repeating unit represented by the formula (8) is not particularly limited, but an integer in which m is an integer between 2 and 1000 is preferable, and an integer of 5 to 600 is particularly preferable. An integer from 10 to 80 is most preferred. When the number of repeating units is within the above range, the workability when the benzoxazole resin precursor is dissolved in a solvent is excellent.

  The polymer composition of the present invention can be obtained by mixing the compound having an amino group and the compound having an active ester group.

  The polymer composition of the present invention can further contain an organic solvent capable of dissolving or dispersing the polymer composition, and the polymer composition can be dissolved in a suitable organic solvent or uniformly dispersed and used as a varnish. Is possible.

As the organic solvent, a solvent that completely dissolves solids is preferable. For example, N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol diester Butyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, Methyl pyruvate, ethyl pyruvate, methyl-3-methoxypropionate, methyl ethyl ketone, methyl isobutyl ketone, Ropentanon, mention may be made of cyclohexanone and tetrahydrofuran. These may use 1 type and may mix and use 2 or more types.
The amount of solvent used in the case of preparing the varnish is not particularly limited as long as it is an amount capable of completely dissolving the polymer composition, and can be appropriately adjusted according to its use. The solvent content in the varnish is preferably about 70 to 95% by weight.

  As a method of using the polymer composition of the present invention, for example, a varnish obtained by dissolving or uniformly dispersing the polymer composition in an organic solvent is used as an appropriate support, such as glass, fiber, metal, silicon wafer, and the like. Apply to ceramic substrate. Examples of the coating method include dipping, screen printing, spraying, spin coating, and roll coating. The coating can be heated and dried after the coating to volatilize the solvent to form a tack-free coating film. Then, it can heat-process and make an amino group and an active ester group react, and it can be set as the film of a crosslinked polymer.

  In the present invention, the heating temperature for producing a crosslinked polymer by crosslinking polymer chains from the polymer composition is preferably 100 ° C. or higher and 350 ° C. or lower, more preferably 100 ° C. or higher and 250 ° C. or lower. is there.

  Examples are given below to illustrate the present invention, but the present invention is not limited thereby.

  The obtained compound was subjected to thermogravimetric analysis for property evaluation. The measurement conditions were as follows.

Thermogravimetric analysis: TG / DTA6200 manufactured by Seiko Instruments Inc. was used, and the temperature was raised from room temperature to 370 ° C. under a temperature increase rate of + 5 ° C./min under a dry nitrogen stream at 200 mL / min. The amount of weight loss when held for 30 minutes was measured.

[Example 1]
(Synthesis of a compound having an amino group)
12.9 g (122 mmol / unit unit) of poly (hydroxyphenylenemethylene) (Mw = 3000, Mn = 980), 36.2 g (146 mmol) of 3-fluoro-6-nitrophenyl benzyl ether, 100 mL of N, N-dimethylformamide To this solution, 42.1 g (304 mmol) of potassium carbonate was added. After stirring at 135 ° C. for 12 hours, the reaction solution was filtered. The filtrate was added dropwise to 2000 mL of ion exchange water. The precipitated solid was washed twice with 2000 mL of methanol and dried under reduced pressure at 50 ° C. for 2 days to obtain 29.9 g of poly ((3-benzyloxy-4-nitrophenoxy) phenylenemethylene) as a yellow solid (yield). (Rate 73.4%).
29.6 g (88.8 mmol / 1 unit unit) of the obtained poly ((3-benzyloxy-4-nitrophenoxy) phenylenemethylene) and 4.96 g (4.66 mmol) of 10% palladium on activated carbon, N, N- After stirring 100 mL of dimethylformamide at room temperature in a hydrogen atmosphere for 36 hours, the reaction solution was filtered. The filtrate was added dropwise to a mixture of 200 mL of methanol and 2000 mL of ion exchange water. The precipitated solid was washed three times with a mixed solution of 200 mL of methanol and 2000 mL of ion-exchanged water, and dried under reduced pressure at 50 ° C. for 2 days to give a poly ((4-amino-3-hydroxyphenoxy) phenylenemethylene) 14 as a brown solid. 0.6 g was obtained (yield 77.1%).
Molecular weight: Mw = 5230, Mn = 1980

  0.4 g of the poly ((4-amino-3-hydroxyphenoxy) phenylenemethylene) obtained above and 0.299 g of diphenyl isophthalate were mixed well in a mortar and subjected to thermogravimetric analysis. The amount of decrease in thermal weight when held for 30 minutes was 0.80% by weight.

[Example 2]
(Synthesis of a compound having an active ester group)
12.9 g (122 mmol / unit unit) of poly (hydroxyphenylenemethylene) (Mw = 3000, Mn = 980), 31.7 g (146 mmol) of 4-fluorobenzoic acid (3-pyridyl), 100 mL of N, N-dimethylformamide To this solution, 42.1 g (304 mmol) of potassium carbonate was added. After stirring at 135 ° C. for 12 hours, the reaction solution was filtered. The filtrate was added dropwise to 2000 mL of ion exchange water. The precipitated solid was washed twice with 2000 mL of methanol and dried under reduced pressure at 50 ° C. for 2 days to obtain 18.0 g of poly ((4- (3-pyridyloxycarbonyl) phenoxy) phenylenemethylene) as a yellow solid.
Molecular weight: Mw = 5630, Mn = 2000

  0.4 g of the poly ((4- (3-pyridyloxycarbonyl) phenoxy) phenylenemethylene) obtained above and 0.093 g of 2,4-diamino-resorcinol were mixed well in a mortar, and thermogravimetric analysis was performed. As a result, the thermogravimetric decrease when held at 370 ° C. for 30 minutes was 0.70% by weight.

[Comparative Example 1]
[Synthesis of poly (methylene-2,6- (1- (2-propinoxy)) phenylene) from poly (methylene-2,6- (1-hydroxy) phenylene)]
Poly (methylene-2,6- (1-hydroxy) phenylene) 22.3 g (210 mmol / 1 unit), propargyl bromide 50.5 g (425 mmol), benzyltriethylammonium chloride 1.45 g (6.37 mmol), tetrahydrofuran While 120 mL was stirred at 50 ° C. in a dry nitrogen atmosphere, potassium hydroxide 60.7 g (1.08 mol) dissolved in ion-exchanged water 60.0 mL was added. The reaction was carried out at 60 ° C. for 6 hours. The reaction solution was heated under reduced pressure to remove propargyl bromide and tetrahydrofuran. The precipitated solid was extracted with 200 mL of ethyl acetate, and the organic layer was washed twice with 500 mL of ion-exchanged water and then poured into 2000 mL of methanol to recover the polymer by reprecipitation. The precipitated solid was dried at 60 ° C. under reduced pressure to obtain 14.7 g of poly (methylene-2,6- (1- (2-propinoxy)) phenylene).
Thermogravimetric analysis of the obtained compound revealed that the thermogravimetric loss when held at 370 ° C. for 30 minutes was 4.30% by weight.

[Comparative Example 2]
[Synthesis of poly (methylene-2,6- (1- (3-phenyl-2-propinoxy)) phenylene) from poly (methylene-2,6- (1- (2-propinoxy)) phenylene)]
3.43 g (23.8 mmol / 1 unit unit) of poly (methylene-2,6- (1- (2-propinoxy)) phenylene) obtained in Comparative Example 1, 6.38 g (31.3 mmol) of benzene iodide, 20.0 mL of pyridine was stirred and dissolved under a dry nitrogen atmosphere. Subsequently, 0.0837 g (0.119 mmol) of dichlorobis (triphenylphosphine) palladium, 0.0956 g (0.364 mmol) of triphenylphosphine, 0.0452 g (0.237 mmol) of copper iodide, and 20 mL of triethylamine were added. Heated at 70 ° C. for 3 hours. The reaction solution was filtered and then added to 1.00 L of methanol to recover the polymer by reprecipitation. The precipitated solid was dried at 60 ° C. under reduced pressure to obtain 4.10 g of poly (methylene-2,6- (1- (3-phenyl-2-propinoxy)) phenylene).
The thermogravimetric analysis of the obtained compound revealed that the thermogravimetric loss when held at 370 ° C. for 30 minutes was 7.11% by weight.

[Comparative Example 3]
[Synthesis of poly (2,6- (3-ethynyl-1-hydroxy) phenylene) from poly (3-ethynylhydroxyphenylenemethylene) from 3-ethynylphenol]
While stirring 5.00 g (42.3 mmol) of 3-ethynylphenol and 10.0 mL of methanol at room temperature, 10.0 mL of a phosphate buffer solution of pH = 7 was added to 2.00 g of horseradish peroxidase. Subsequently, 28.8 mL (42.3 mmol) of 5 wt% hydrogen peroxide was added dropwise over 3 hours, and the mixture was further stirred at room temperature for 3 hours. The precipitate was centrifuged from the reaction solution, stirred in 50 mL of methanol and 50 mL of ion exchange water, and washed. The obtained solid was dried under reduced pressure to obtain 3.25 g of poly (2,6- (3-ethynyl-1-hydroxy) phenylene).
The thermogravimetric analysis of the obtained compound revealed that the thermogravimetric loss when kept at 370 ° C. for 30 minutes was 8.72% by weight.
As is clear from the above, it was shown that the crosslinked polymer provided by the present invention is excellent in heat resistance even at 370 ° C.

  Since the crosslinked polymer obtained by the present invention exhibits excellent heat resistance even in a high temperature range of 350 ° C. or higher, it can be suitably used in fields requiring a material process at a high temperature. Applications are suitably used for electronic materials, automotive members, engineering materials, structural members, adhesives, coating film forming materials, insulating materials, antioxidant materials, recording materials, and the like.

Claims (9)

  A polymer composition comprising a compound having an amino group and a compound having an active ester group, wherein at least one of the compound having an amino group and the compound having an active ester group is a polymer. A polymer composition. The polymer composition according to claim 1, wherein the active ester group is represented by the following general formula (1).

(In the formula (1), R represents an alkyl group, a pyridyl group, a quinolyl group, an aromatic group, or a benzotriazole group, and a hydrogen atom in these groups may be substituted with at least one organic group. .) The polymer composition according to claim 1 or 2, wherein the compound having an amino group has a repeating unit represented by the following general formula (2).

(Ar in the formula represents an aromatic group. X represents a group composed of at least one group selected from an aliphatic group, an aromatic group, a sulfonyl group and an oxygen atom. m represents an integer of 2 or more and 10,000 or less, and n in the formula represents an integer of 1 or more and 3 or less. The polymer composition according to any one of claims 1 to 3, wherein the compound having an amino group is represented by the following general formula (3).

(Ar in the formula represents an aromatic group. In the formula, a represents an integer of 1 or more and 6 or less.) The polymer composition according to any one of claims 2 to 4, wherein the compound having an active ester group has a repeating unit represented by the following general formula (4).

[In Formula (4), -COOR may have 1 to 5 on the same benzene ring. Ar represents an aromatic group. X represents a group composed of at least one group selected from an aliphatic group, an aromatic group, a sulfonyl group, and an oxygen atom. M in the formula represents an integer of 2 or more and 10,000 or less. N in the formula represents an integer of 1 or more and 3 or less. ] The polymer composition according to any one of claims 2 to 5, wherein the compound having an active ester group is represented by the following general formula (5).

(Ar in the formula represents an aromatic group. In the formula, a represents an integer of 1 or more and 6 or less.)   The polymer composition according to any one of claims 1 to 6, wherein the compound having an active ester group is a benzoxazole resin precursor.   The polymer composition according to any one of claims 1 to 7, comprising an organic solvent capable of dissolving or dispersing the polymer composition.   A crosslinked polymer that can be obtained by crosslinking the polymer chain by reacting the polymer composition according to claim 1.