JP5095300B2 - N-substituted benzimidazole ring-containing bridged alicyclic compound, N-substituted benzimidazole ring-containing polymer, thin film, and method for producing the same - Google Patents

Description

  INDUSTRIAL APPLICABILITY The present invention is a thin film such as an insulating film used in the manufacture of semiconductors, particularly a thin film such as an insulating film having characteristics of heat resistance, low hygroscopicity, and low relative dielectric constant, a method for manufacturing the same, and a useful method for obtaining the thin film The present invention relates to a monomer, a polymer obtained from the monomer, and a film-forming material containing them.

  2. Description of the Related Art In recent years, in a semiconductor process in which circuit patterns are becoming finer, a lower dielectric constant of an interlayer insulating film is required. It is said that the construction of a hole structure is effective for lowering the dielectric constant of an interlayer insulating film. For silicon oxide-based interlayer insulating films, introduction of a hole structure using a foaming agent or the like has been proposed. . However, although this method can form vacancies, it is difficult to avoid linking of vacancies (continuation of vacancies), so there are difficulties in mechanical strength and thermal stability. The process had serious problems such as film breakage.

  The inventors of the present invention have found that an insulating film having pores at a molecular level formed by polymerization of a polyfunctional crosslinkable monomer can achieve both low dielectric constant and high mechanical strength ( For example, refer to Japanese Patent Application Laid-Open No. 2004-307804). However, when the insulating film is left in the air, there is a problem that the value of the flowing current increases due to moisture absorption of the thin film. Further, in the current situation where higher integration of semiconductors is progressing, there is a demand for further reduction in relative dielectric constant.

JP 2004-307804 A

  An object of the present invention is to provide a thin film such as an insulating film having a high heat resistance and a low relative dielectric constant useful for manufacturing a semiconductor and having a low hygroscopicity and a manufacturing method thereof, a monomer capable of forming these, It is to provide a polymer and a film forming material containing them.

  As a result of intensive studies to achieve the above object, the present inventors have found that when a thin film is formed from a compound or polymer having a bridged alicyclic skeleton and an N-substituted benzimidazole ring, the relative permittivity is low and the hygroscopic property is low. The inventors found that an extremely low thin film can be obtained and completed the present invention.

（式中、Ｚはアダマンタン−１，３，５，７−テトライル基を示し、Ｙ¹は単結合又はアリレン（arylene）基を示し、Ｙ²は単結合又は下記式

（式中、Ｒ ² は炭素数１〜５０の２価の脂肪族炭化水素基を示す。Ｒ′は水素原子又は下記式

（式中、Ｒ ¹ は単結合又は炭素数１〜５０の２価の脂肪族炭化水素基を示す。ｊは０〜３の整数を示す）
から選ばれる基を示す。各式において、結合の左右の向きは問わない）
から選ばれる２価の基又はこれらが２以上結合した２価の基を示し、Ｘは水素原子、又は、炭素数１〜１０のアルキル基、炭素数６〜２０のアリール基及びトリアルキルシリル基から選択された置換基を有していてもよいエチニル基を示し、Ｒ^aは水素原子又は炭化水素基を示す。Ａは、下記式（ａ）

（式中、Ｒは下記式

（式中、Ｒ ¹ は単結合又は炭素数１〜５０の２価の脂肪族炭化水素基を示す。ｊは０〜３の整数を示す）
から選ばれる基を示す。式（ａ）において、左側がＹ¹と結合する側、右側がＹ²と結合する側である）
で表される基を示す。ｎは３又は４、ｍは０又は１、ｋは０〜２の整数を示す。ｎ＋ｍ＝４である。分子内の複数のＹ¹、Ｙ² 、Ａ、Ｒ及び複数存在する場合のＸは、それぞれ同一であっても異なっていてもよい）
で表されるＮ−置換ベンズイミダゾール環含有有橋脂環式化合物を提供する。 That is, the present invention provides the following formula (1 ′ )

(In the formula, Z represents an adamantane-1,3,5,7-tetrayl group , Y ¹ represents a single bond or an arylene group , and Y ² represents a single bond or the following formula:

(Wherein R ² represents a divalent aliphatic hydrocarbon group having 1 to 50 carbon atoms. R ′ represents a hydrogen atom or the following formula:

(In the formula, R ¹ represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 50 carbon atoms. J represents an integer of 0 to 3)
Represents a group selected from: In each formula, the right and left direction of the bond does not matter)
Or a divalent group in which two or more of these are bonded , and X is a hydrogen atom , an alkyl group having 1 to 10 carbon atoms , an aryl group having 6 to 20 carbon atoms , or a trialkylsilyl group. Represents an ethynyl group optionally having a substituent selected from R ^a represents a hydrogen atom or a hydrocarbon group. A is the following formula (a )

(Where R is the following formula

(In the formula, R ¹ represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 50 carbon atoms. J represents an integer of 0 to 3)
Represents a group selected from: In the formula (a), the left side is the side bonded to Y ^1, and the right side is the side bonded to Y ² )
The group represented by these is shown. n is 3 or 4 , m is 0 or 1 , and k is an integer of 0-2. n + m = 4 . And a plurality of Y ¹ , Y ² , A ¹ , R in the molecule and X in the case where there are a plurality thereof may be the same or different)
The N-substituted benzimidazole ring-containing bridged alicyclic compound represented by these is provided.

The present invention also provides the N-substituted benzimidazole ring-containing bridged alicyclic compound [ wherein k in the formula (1 ′) is 1 or 2, and X is an alkyl group having 1 to 10 carbon atoms. Represents an ethynyl group optionally having a substituent selected from an aryl group having 6 to 20 carbon atoms and a trialkylsilyl group.] The weight average molecular weight obtained by polymerizing A ′ is 200 to 100,000. An N-substituted benzimidazole ring-containing polymer is provided.

［式中、Ｚはアダマンタン−１，３，５，７−テトライル基を示し、Ｙ¹は単結合又はアリレン（arylene）基を示し、Ｙ²は単結合又は下記式

（式中、Ｒ ² は炭素数１〜５０の２価の脂肪族炭化水素基を示す。Ｒ′は水素原子又は下記式

（式中、Ｒ ¹ は単結合又は炭素数１〜５０の２価の脂肪族炭化水素基を示す。ｊは０〜３の整数を示す）
から選ばれる基を示す。各式において、結合の左右の向きは問わない）
から選ばれる２価の基又はこれらが２以上結合した２価の基を示し、Ｒ^aは水素原子又は炭化水素基を示す。Ａは、下記式（ａ）

（式中、Ｒは下記式

（式中、Ｒ ¹ は単結合又は炭素数１〜５０の２価の脂肪族炭化水素基を示す。ｊは０〜３の整数を示す）
から選ばれる基を示す。式（ａ）において、左側がＹ¹と結合する側、右側がＹ²と結合する側である）
で表される基を示す）
で表される繰り返し単位を有し、重量平均分子量が２００〜１０００００であるＮ−置換ベンズイミダゾール環含有重合体を提供する。 The present invention further includes the following formula ( 5b) or (5c):

[ Wherein Z represents an adamantane-1,3,5,7-tetrayl group , Y ¹ represents a single bond or an arylene group , and Y ² represents a single bond or the following formula:

(Wherein R ² represents a divalent aliphatic hydrocarbon group having 1 to 50 carbon atoms. R ′ represents a hydrogen atom or the following formula:

(In the formula, R ¹ represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 50 carbon atoms. J represents an integer of 0 to 3)
Represents a group selected from: In each formula, the right and left direction of the bond does not matter)
Or a divalent group in which two or more of these are bonded , and Ra represents ^a hydrogen atom or a hydrocarbon group. A is the following formula (a )

(Where R is the following formula

(In the formula, R ¹ represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 50 carbon atoms. J represents an integer of 0 to 3)
Represents a group selected from: In the formula (a), the left side is the side bonded to Y ^1, and the right side is the side bonded to Y ² )
Represents a group represented by
Have a in the repeating unit represented by weight average molecular weight to provide a certain N- substituted benzimidazole ring-containing polymer at from 200 to 100,000.

  The present invention further provides a film-forming material in which the N-substituted benzimidazole ring-containing bridged alicyclic compound is dissolved in a solvent.

  The present invention further provides a film-forming material in which the N-substituted benzimidazole ring-containing polymer is dissolved in a solvent.

  The present invention further provides a method for producing a thin film, wherein the film forming material is applied to a substrate and dried or reacted by heating to form a thin film.

（式中、Ｚは有橋脂環骨格を示し、Ｙ ¹ は単結合又は２価の有機基を示し、Ｙ ² は単結合又は２〜３価の有機基を示し、Ｘは水素原子又は反応性官能基を示し、Ｒ ^a は水素原子又は炭化水素基を示す。Ａは、下記式（ａ）又は（ｂ）

（式中、Ｒは１価の有機基を示す。何れの式も、左側がＹ ¹ と結合する側、右側がＹ ² と結合する側である）
で表される基を示す。ｎは２〜７の整数、ｍは０〜５の整数、ｋは０〜２の整数を示す。ｎ＋ｍ＝２〜７である。分子内の複数のＹ ¹ 、Ｙ ² 、Ｘ、Ａ、Ｒ及び複数存在する場合のＸ、Ｒ ^a は、それぞれ同一であっても異なっていてもよい）
で表されるＮ−置換ベンズイミダゾール環含有有橋脂環式化合物。
［２］Ｚにおける有橋脂環骨格に係る有橋脂環が下記式から選ばれる環、又はこれらが２以上結合した環である前記［１］記載のＮ−置換ベンズイミダゾール環含有有橋脂環式化合物。

［３］Ｒにおける１価の有機基が、脂肪族炭化水素基、脂環式炭化水素基、芳香族炭化水素基、又はこれらの２以上が、酸素原子若しくは硫黄原子を介して又は介することなく結合した基である前記［１］又は［２］記載のＮ−置換ベンズイミダゾール環含有有橋脂環式化合物。
［４］Ｒにおける１価の有機基が、下記式から選ばれる基である前記［１］〜［３］の何れかに記載のＮ−置換ベンズイミダゾール環含有有橋脂環式化合物。

（式中、Ｒ ¹ は単結合又は炭素数１〜５０の２価の脂肪族炭化水素基を示す。ｊは０〜３の整数を示す）
［５］Ｙ ¹ 、Ｙ ² における２価の有機基が、アルキレン基、アルケニレン基、アルキニレン基、２価の脂環式炭化水素基、アリレン基、２価の複素環式基、もしくはこれらの２価の有機基が２以上結合した基、又はこれらの２価の有機基の１又は２以上と、酸素原子（−Ｏ−）、硫黄原子（−Ｓ−）から選択された少なくとも１つの原子とが結合した基である前記［１］〜［４］の何れかに記載のＮ−置換ベンズイミダゾール環含有有橋脂環式化合物。
［６］Ｙ ¹ 、Ｙ ² における２価の有機基が、下記式から選ばれる２価の基、又はこれらが２以上結合した２価の基である前記［１］〜［５］の何れかに記載のＮ−置換ベンズイミダゾール環含有有橋脂環式化合物。

（式中、Ｒ ² は炭素数１〜５０の２価の脂肪族炭化水素基を示す。Ｒ′は水素原子又は１価の有機基を示す。各式において、結合の左右の向きは問わない）
［７］Ｘにおける反応性官能基が、置換基を有していてもよいエチニル基、置換基を有していてもよいビニル基、ハロゲン原子、無置換又はモノ置換アミノ基、ハロホルミル基、酸無水物基、酸アジド基、ヒドラジド基、シアノ基、アシル基、カルボキシル基、置換オキシカルボニル基、ヒドロキシル基、メルカプト基、イミン基及びアルコキシシリル基から選択された基である前記［１］〜［６］の何れかに記載のＮ−置換ベンズイミダゾール環含有有橋脂環式化合物。
［８］前記［１］〜［７］の何れかに記載のＮ−置換ベンズイミダゾール環含有有橋脂環式化合物［但し、式（１）中のｋは１又は２である］Ａを重合して得られるＮ−置換ベンズイミダゾール環含有重合体。
［９］前記［１］〜［７］の何れかに記載のＮ−置換ベンズイミダゾール環含有有橋脂環式化合物［但し、式（１）中のｋは１又は２である］Ａと、前記Ｎ−置換ベンズイミダゾール環含有有橋脂環式化合物Ａ中の反応性官能基Ｘに対して反応性を有する官能基又は官能基群を２以上有する多官能化合物Ｂとの反応により得られるＮ−置換ベンズイミダゾール環含有重合体。
［１０］下記式（５ａ）、（５ｂ）又は（５ｃ）

［式中、Ｚは有橋脂環骨格を示し、Ｙ ¹ は単結合又は２価の有機基を示し、Ｙ ² は単結合又は２価の有機基を示し、Ｒ ^a は水素原子又は炭化水素基を示す。Ａは、下記式（ａ）又は（ｂ）

（式中、Ｒは１価の有機基を示す。何れの式も、左側がＹ ¹ と結合する側、右側がＹ ² と結合する側である）
で表される基を示す］
で表される繰り返し単位を有するＮ−置換ベンズイミダゾール環含有重合体。
［１１］重量平均分子量が２００〜１０００００である前記［８］〜［１０］の何れかに記載のＮ−置換ベンズイミダゾール環含有重合体。
［１２］前記［１］〜［７］の何れかに記載のＮ−置換ベンズイミダゾール環含有有橋脂環式化合物を溶媒に溶解させた膜形成材料。
［１３］前記［１］〜［７］の何れかに記載のＮ−置換ベンズイミダゾール環含有有橋脂環式化合物［但し、式（１）中のｋは１又は２である］Ａと、前記Ｎ−置換ベンズイミダゾール環含有有橋脂環式化合物Ａ中の反応性官能基Ｘに対して反応性を有する官能基又は官能基群を２以上有する多官能化合物Ｂとを溶媒に溶解させた膜形成材料。
［１４］前記［８］〜［１１］の何れ項に記載のＮ−置換ベンズイミダゾール環含有重合体を溶媒に溶解させた膜形成材料。
［１５］前記［１２］〜［１４］の何れかに記載の膜形成材料を基板上に塗布し、乾燥させるか、又は加熱により反応させて、薄膜を形成することを特徴とする薄膜の製造方法。
［１６］前記［１５］記載の薄膜の製造方法により形成された薄膜。 The present invention further provides a thin film formed by the above-described thin film manufacturing method.
In this specification, in addition to the above invention, the following invention is also described.
[1] The following formula (1)

(In the formula, Z represents a bridged alicyclic skeleton, Y ¹ represents a single bond or a divalent organic group, Y ² represents a single bond or a divalent organic group, and X represents a hydrogen atom or a reaction. R ^a represents a hydrogen atom or a hydrocarbon group, A represents the following formula (a) or (b)

(In the formula, R represents a monovalent organic group. In any formula, the left side is the side bonded to Y ^1, and the right side is the side bonded to Y ² )
The group represented by these is shown. n is an integer of 2 to 7, m is an integer of 0 to 5, and k is an integer of 0 to 2. n + m = 2-7. And a plurality of Y ¹ , Y ² , X, A, R in the molecule and X and R ^{a in the} case where a plurality exist may be the same or different)
An N-substituted benzimidazole ring-containing bridged alicyclic compound represented by the formula:
[2] The N-substituted benzimidazole ring-containing bridged fat according to the above [1], wherein the bridged alicyclic ring related to the bridged alicyclic skeleton in Z is a ring selected from the following formulas or a ring in which two or more of these are bonded: Cyclic compounds.

[3] The monovalent organic group in R is an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or two or more of these are either through or without an oxygen atom or a sulfur atom. The N-substituted benzimidazole ring-containing bridged alicyclic compound according to [1] or [2], which is a bonded group.
[4] The N-substituted benzimidazole ring-containing bridged alicyclic compound according to any one of [1] to [3], wherein the monovalent organic group in R is a group selected from the following formulae.

(In the formula, R ¹ represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 50 carbon atoms. J represents an integer of 0 to 3)
[5] The divalent organic group in Y ¹ and Y ² is an alkylene group, alkenylene group, alkynylene group, divalent alicyclic hydrocarbon group, arylene group, divalent heterocyclic group, or these 2 A group in which two or more valent organic groups are bonded, or one or more of these divalent organic groups, and at least one atom selected from an oxygen atom (—O—) and a sulfur atom (—S—) The N-substituted benzimidazole ring-containing bridged alicyclic compound according to any one of the above [1] to [4], which is a group to which is bonded.
[6] Any of the above [1] to [5], wherein the divalent organic group in Y ¹ and Y ² is a divalent group selected from the following formulas or a divalent group in which two or more of these are bonded. N-substituted benzimidazole ring-containing bridged alicyclic compounds described in 1.

(In the formula, R ² represents a divalent aliphatic hydrocarbon group having 1 to 50 carbon atoms. R ′ represents a hydrogen atom or a monovalent organic group. In each formula, the right and left direction of the bond does not matter. )
[7] The reactive functional group in X may have an optionally substituted ethynyl group, an optionally substituted vinyl group, a halogen atom, an unsubstituted or monosubstituted amino group, a haloformyl group, an acid [1] to [1], which are groups selected from an anhydride group, acid azide group, hydrazide group, cyano group, acyl group, carboxyl group, substituted oxycarbonyl group, hydroxyl group, mercapto group, imine group and alkoxysilyl group 6] The N-substituted benzimidazole ring-containing bridged alicyclic compound according to any one of [6].
[8] The N-substituted benzimidazole ring-containing bridged alicyclic compound according to any one of [1] to [7] above, wherein k in formula (1) is 1 or 2; N-substituted benzimidazole ring-containing polymer.
[9] The N-substituted benzimidazole ring-containing bridged alicyclic compound according to any one of [1] to [7] above, wherein k in formula (1) is 1 or 2, and N obtained by reaction with a polyfunctional compound B having two or more functional groups or functional groups having reactivity with the reactive functional group X in the N-substituted benzimidazole ring-containing bridged alicyclic compound A -Substituted benzimidazole ring-containing polymer.
[10] The following formula (5a), (5b) or (5c)

[In the formula, Z represents a bridged alicyclic skeleton, Y ¹ represents a single bond or a divalent organic group, Y ² represents a single bond or a divalent organic group, and R ^a represents a hydrogen atom or a hydrocarbon. Indicates a group. A is the following formula (a) or (b)

(In the formula, R represents a monovalent organic group. In any formula, the left side is the side bonded to Y ^1, and the right side is the side bonded to Y ² )
Indicates a group represented by
The N-substituted benzimidazole ring containing polymer which has a repeating unit represented by these.
[11] The N-substituted benzimidazole ring-containing polymer according to any one of [8] to [10], which has a weight average molecular weight of 200 to 100,000.
[12] A film forming material obtained by dissolving the N-substituted benzimidazole ring-containing bridged alicyclic compound according to any one of [1] to [7] in a solvent.
[13] The N-substituted benzimidazole ring-containing bridged alicyclic compound according to any one of [1] to [7] above, wherein k in formula (1) is 1 or 2, The polyfunctional compound B having two or more functional groups or functional groups having reactivity with the reactive functional group X in the N-substituted benzimidazole ring-containing bridged alicyclic compound A was dissolved in a solvent. Film forming material.
[14] A film-forming material in which the N-substituted benzimidazole ring-containing polymer according to any one of [8] to [11] is dissolved in a solvent.
[15] Production of a thin film, wherein the film forming material according to any one of [12] to [14] is applied onto a substrate and dried or reacted by heating to form a thin film Method.
[16] A thin film formed by the method for producing a thin film according to [15].

  Since the N-substituted benzimidazole ring-containing polymer of the present invention has a bridged alicyclic skeleton as a central skeleton and a structural unit having an N-substituted benzimidazole ring as a repeating unit, it is bonded to the nitrogen atom. A thin film having extremely low hygroscopicity and a low relative dielectric constant can be formed due to the polar restraining effect and the steric exclusion effect of the substituent. This thin film is excellent in heat resistance and mechanical strength.

The N-substituted benzimidazole ring-containing bridged alicyclic compound of the present invention is represented by the formula (1). In the formula, Z represents a bridged alicyclic skeleton, Y ¹ represents a single bond or a divalent organic group, Y ² represents a single bond or a bivalent to trivalent organic group, and X represents a reactive functional group. R ^a represents a hydrogen atom or a hydrocarbon group. A represents a group represented by the formula (a) or (b). In the formula (a) or (b), R represents a monovalent organic group. Further, in both formulas (a) and (b), the left side is the side where Y ¹ is coupled, and the right side is the side where Y ² is coupled.

  Representative examples of the bridged alicyclic skeleton as the central skeleton Z include rings represented by the above formulas (2a) to (2j), or rings in which two or more (for example, 2 to 3) are bonded. .

  Preferred examples of the bridged alicyclic skeleton include an adamantane skeleton (adamantane-1,3,5,7-tetrayl group, etc.), a biadamantane skeleton, a tetraphenyladamantane skeleton, a norbornane skeleton, a tetramethylnorbornane skeleton, a norbornene skeleton, Examples include a tetramethylnorbornene skeleton. The molecular weight of the central skeleton is, for example, about 40 to 1460, preferably about 60 to 500.

Examples of the divalent organic group for Y ¹ and Y ² include an alkylene group, an alkenylene group, an alkynylene group, a divalent alicyclic hydrocarbon group, an arylene group, a divalent heterocyclic group, or these 2 groups. A group in which two or more (for example, 2 to 5) valent organic groups are bonded, or one or more (for example, 1 to 5) of these divalent organic groups, an oxygen atom (—O—), and a sulfur atom And a group in which at least one atom selected from (-S-) is bonded. Examples of the trivalent organic group for Y ² include trivalent organic groups corresponding to the above divalent organic groups.

  Examples of the alkylene group include linear or branched chains having 1 to 10 carbon atoms such as methylene, ethylene, ethylidene, trimethylene, isopropylidene, propylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, and decamethylene groups ( A linear alkylene group is preferable. Examples of the alkenylene group include linear or branched (preferably linear) alkenylene groups having 2 to 10 carbon atoms such as vinylene and propenylene groups. Examples of the alkynylene group include linear or branched (preferably linear) alkynylene groups having 2 to 10 carbon atoms such as ethynylene and propynylene groups.

  Examples of the divalent alicyclic hydrocarbon group include cycloalkylene groups such as cyclopentylene, cyclohexylene, cyclopentylidene, and cyclohexylidene groups, and cycloalkylidene groups; adamantane-1,3-diyl groups, 1,3 -Divalent bridged alicyclic group such as dimethyladamantane-5,7-diyl group. Examples of the arylene group include phenylene, benzylidene, naphthylene, and anthranylene group.

  Examples of the heterocyclic ring related to the divalent heterocyclic group include a benzimidazole ring (which may have a substituent on the nitrogen atom), a benzoxazole ring, a benzthiazole ring, and an imidazole ring (a substituent on the nitrogen atom). An oxazole ring, a thiazole ring, and the like.

  Examples of the divalent group in which these divalent organic groups and oxygen atoms are bonded include, for example, an oxyalkylene group having about 1 to 10 carbon atoms such as an oxyethylene group, and a polyoxyalkylene group having about 2 to 10 carbon atoms. And a divalent group derived by removing two hydrogen atoms from diphenyl ether.

As a typical example of the divalent organic group in Y ¹ and Y ² , a divalent group selected from the above formulas (4a) to (4n) or two or more (for example, 2 to 5) of these are bonded. Valent groups. Each ring in the formula may have a substituent. As a substituent, a C1-C50 hydrocarbon group etc. are mentioned, for example.

In the formula, R ² represents a divalent aliphatic hydrocarbon group having 1 to 50 carbon atoms (preferably 1 to 20 carbon atoms). Examples of the divalent aliphatic hydrocarbon group include methylene, ethylene, ethylidene, trimethylene, propylene, isopropylidene, tetramethylene, ethylethylene, hexamethylene, decamethylene, dodecamethylene, vinylene, propenylene, hexenylene, octenylene, propynylene group, and the like. And a linear or branched alkylene group, alkenylene group, and alkynylene group.

R ′ represents a hydrogen atom or a monovalent organic group. As said monovalent organic group, the same thing as the monovalent organic group in R mentioned later is mentioned. As a typical example of the trivalent organic group in Y ² , a trivalent organic group corresponding to the typical example of the above divalent organic group can be given.

  Examples of the reactive functional group in X include an ethynyl group which may have a substituent, a vinyl group which may have a substituent, a halogen atom, an unsubstituted or monosubstituted amino group, a haloformyl group, Examples include acid anhydride groups, acid azide groups, hydrazide groups, cyano groups, acyl groups, carboxyl groups, substituted oxycarbonyl groups, hydroxyl groups, mercapto groups, imine groups, and alkoxysilyl groups.

  Examples of the substituent in the ethynyl group which may have a substituent include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, and isobutyl groups (for example, alkyl groups having about 1 to 10 carbon atoms); Examples thereof include aryl groups such as phenyl and naphthyl groups (for example, aryl groups having about 6 to 20 carbon atoms); substituted silyl groups such as trimethylsilyl and triethylsilyl groups (for example, trialkylsilyl groups).

  Examples of the substituent in the vinyl group which may have a substituent include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, and isobutyl groups (for example, alkyl groups having about 1 to 10 carbon atoms); Examples thereof include aryl groups such as phenyl and naphthyl groups (for example, aryl groups having about 6 to 20 carbon atoms).

The mono-substituted amino group, for example, an alkylamino group such as methylamino group, ethylamino group; and the like aralkylamino group such as benzylamino group; arylamino groups such as phenylamino group.

Examples of the haloformyl group include —COCl, —COBr, —COI and the like. As an acyl group, C1-C10 acyl groups, such as a formyl group, an acetyl group, a propionyl group, a benzoyl group, etc. are mentioned, for example. Examples of the substituted oxycarbonyl group include alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group ( _C1-4 alkoxy-carbonyl group etc.); aryloxycarbonyl groups such as phenoxycarbonyl group; aralkyl such as benzyloxycarbonyl group An oxycarbonyl group and the like are included. The imine group includes a group formed by reacting the acyl group with ammonia or an amine (for example, an amine having about 1 to 10 carbon atoms such as methylamine, ethylamine or aniline). Examples of the alkoxysilyl group include trialkylsilyl groups such as trimethylsilyl group and triethylsilyl group.

  The monovalent organic group in R includes, for example, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or two or more of these (for example, 2 to 4) each having an oxygen atom or a sulfur atom. Included are groups attached through or without. The total carbon number of the monovalent organic group is, for example, 1 to 50, preferably 2 to 40.

  Examples of the aliphatic hydrocarbon group include 1 to 40 carbon atoms (preferably 1 to 1) such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, decyl, and dodecyl groups. 30 or more preferably 1 to 25) linear or branched alkyl group; 2 to 40 carbon atoms (preferably 2 to 30) such as vinyl, allyl, 1-butenyl, 3-methyl-4-pentenyl group, etc. , More preferably 2 to 25) linear or branched alkenyl group; ethynyl, propynyl, 1-butynyl, 2-butynyl group and the like having 2 to 40 carbon atoms (preferably 2 to 30, more preferably 2). About 25 to 25 linear or branched alkynyl groups.

  Examples of the alicyclic hydrocarbon group include a cycloalkyl group having about 3 to 20 members (preferably 3 to 15 members, more preferably 3 to 12 members) such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups. , Monocyclic alicyclic hydrocarbon groups such as cycloalkenyl groups of about 3 to 20 members (preferably 3 to 15 members, more preferably 3 to 10 members) such as cyclopropenyl, cyclobutenyl, cyclopentenyl and cyclohexenyl groups Adamantane ring, perhydroindene ring, decalin ring, perhydrofluorene ring, perhydroanthracene ring, perhydrophenanthrene ring, tricyclodecane ring, tricycloundecane ring, tetracyclododecane ring, perhydroacenaphthene ring, perhydro Phenalene ring, norbornane ring, norbol Such bridged alicyclic hydrocarbon group having such bridged alicyclic about 2-4 rings such as down ring (bridged ring hydrocarbon group). Examples of the aromatic hydrocarbon group include aromatic hydrocarbon groups having about 6 to 20 carbon atoms (preferably 6 to 14) such as phenyl, biphenyl, naphthyl, anthranyl, phenanthryl, and pyrenyl groups.

The hydrocarbon group in which an aliphatic hydrocarbon group and an alicyclic hydrocarbon group are bonded includes a cycloalkyl-alkyl group such as cyclopentylmethyl, cyclohexylmethyl, 2-cyclohexylethyl group (for example, C _3-20 cycloalkyl- C _1-4 alkyl group, etc.); bridged alicyclic group-alkyl group such as adamantylmethyl, adamantylethyl, norbornylmethyl, norbornylethyl group and the like. The hydrocarbon group in which an aliphatic hydrocarbon group and an aromatic hydrocarbon group are bonded includes, for example, an aralkyl group such as benzyl, 2-phenylethyl, or biphenylmethyl group (for example, a C _7-18 aralkyl group). An alkyl-substituted aryl group (for example, a phenyl group or a naphthyl group substituted with about 1 to 4 C _1-4 alkyl groups) and the like.

  The aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, and a group in which these groups are bonded may have a substituent. The substituent is not particularly limited as long as it does not impair the physical properties of the high molecular weight polymer after reaction or polymerization.

Representative examples of the monovalent organic group for R include groups selected from the above formulas (3a) to (3i). In the formula, R ¹ represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 50 (preferably 1 to 39) carbon atoms. j represents an integer of 0 to 3. Examples of the divalent aliphatic hydrocarbon group having 1 to 50 carbon atoms in R ¹ include the same groups as the divalent aliphatic hydrocarbon group having 1 to 50 carbon atoms in R ² . Each ring in the formula may have a substituent. As a substituent, a C1-C50 hydrocarbon group etc. are mentioned, for example.

As the hydrocarbon group for R ^a, for example, aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and the like of these attached groups. Examples of the aliphatic hydrocarbon group, the alicyclic hydrocarbon group, the aromatic hydrocarbon group, and the group in which these are bonded include the groups exemplified in the above R.

In formula (1), n is an integer of 2 to 7 (preferably 3 or 4, more preferably 4), m is an integer of 0 to 5, and k is an integer of 0 to 2. n + m = 2-7. A plurality of Y ¹ , Y ² , X, A, R in the molecule and X and R ^{a in the} case where a plurality exist may be the same or different.

The compound represented by the formula (1) can be synthesized using a known compound or a derivative derived from the known compound as a starting material by using a reaction such as a condensation reaction, a substitution reaction, an addition reaction, an oxidation reaction, or a cyclization reaction. . For example, in the compound represented by the formula (1), a halogen compound: RX ¹ (X ¹ is a halogen atom) in the presence of a base in a corresponding compound in which R in the formula (a) or the formula (b) is a hydrogen atom. R can be obtained by reacting the same as above. As the base, for example, sodium hydride can be used. The reaction is carried out using a solvent [for example, amides such as N, N-dimethylacetamide (DMAc) and N-methyl-2-pyrrolidone; cyclic aminoacetals such as dimethylimidazolidine and dimethylimidazolidinone (dimethylimidazolidine-dione). Etc.] can be performed at a temperature of about -20 ° C to 120 ° C. The benzimidazole skeleton in the compound used as a raw material in this reaction is an aldehyde compound and a diamine compound in which two amino groups are bonded to the ortho position of the benzene ring in a solvent (for example, the solvent exemplified above) in an oxygen atmosphere. It can form by making it react at the temperature of about -30 degreeC-150 degreeC.

  The N-substituted benzimidazole ring-containing polymer of the present invention includes (i) the N-substituted benzimidazole ring-containing bridged alicyclic compound [wherein k in formula (1) is 1 or 2] A A polymer obtained by polymerizing (hereinafter, simply referred to as “compound A”), (ii) a functional group or function having reactivity with the reactive functional group X in the compound A and the compound A A polymer obtained by a reaction with a polyfunctional compound B having two or more groups (hereinafter sometimes simply referred to as “compound B”), and (iii) the above formula (5a), (5b) or (5c) N-substituted benzimidazole ring-containing polymers having a repeating unit represented by the formula: The weight average molecular weight of the N-substituted benzimidazole ring-containing polymer of the present invention is, for example, 200 to 100,000, preferably 1000 to 80000, and more preferably 5000 to 60000.

  The polymer (i) is obtained when X in the compound A is a functional group having self-reactivity (a functional group in which X reacts with each other; for example, an ethynyl group which may have a substituent). be able to. The compound A to be polymerized may be one type or two or more types.

  When the polymer (ii) is produced, as the functional group having reactivity with the reactive functional group X in the compound A in the compound B, known ones can be used. For example, when the reactive functional group X of the compound A is an ethynyl group which may have a substituent, examples of the reactive functional group of the compound B include an ethynyl group which may have a substituent. . When the reactive functional group X of the compound A is a halogen atom, a haloformyl group, an acid anhydride group, a carboxyl group, or a substituted oxycarbonyl group, the reactive functional group of the compound B is an unsubstituted or monosubstituted amino group, a hydroxyl group And a mercapto group. When the reactive functional group X of Compound A is an unsubstituted or monosubstituted amino group, hydroxyl group, or mercapto group, the reactive functional group of Compound B is a halogen atom, haloformyl group, acid anhydride group, carboxyl group, substituted An oxycarbonyl group, an acyl group, etc. are mentioned. When the reactive functional group X of the compound A is an acyl group, the reactive functional group of the compound B includes an amino group. In addition, when the reactive functional group X of the compound A is an alkoxysilyl group, examples of the reactive functional group of the compound B include an alkoxysilyl group.

  In addition, when the combination of the reactive functional group X of the compound A and the reactive functional group of the compound B is as follows, a heterocyclic ring is formed by the reaction. That is, one of the reactive functional group of Compound A and the reactive functional group of Compound B is a carboxyl group, a substituted oxycarbonyl group, a haloformyl group, or a formyl group, and the other two amino groups bonded to adjacent carbon atoms. In the case of a group, an imidazole ring or the like (a benzimidazole ring in the case of two amino groups bonded to the ortho-position carbon atom of the benzene ring) is formed, one of which is a carboxyl group, a substituted oxycarbonyl group, a haloformyl Group or formyl group, and the other is an amino group and a hydroxyl group bonded to adjacent carbon atoms, an oxazole ring or the like (the other is an amino group and a hydroxyl group bonded to a carbon atom at the ortho position of the benzene ring) A benzoxazole ring), one of which is a carboxyl group, a substituted oxycarbonyl group, a haloformyl Or a formyl group in which the other is an amino group and a mercapto group bonded to adjacent carbon atoms, a thiazole ring or the like (in the case where the other is an amino group and a mercapto group bonded to a carbon atom in the ortho position of the benzene ring) Form a benzthiazole ring).

  Compound B is preferably a bifunctional to tetrafunctional compound. Representative examples of compound B include, for example, 1,2,4,5-tetraaminobenzene, 1,4-diamino-2,5-dihydroxybenzene, 1,5-diamino-2,4-dihydroxybenzene, 1 , 4-diamino-2,5-dimercaptobenzene, 1,5-diamino-2,4-dimercaptobenzene 3,3′-diaminobenzidine and the like. These compounds can be used when the reactive functional group X of the compound A is a carboxyl group, a substituted oxycarbonyl group, a haloformyl group, or a formyl group, and the above heterocycle is formed by the reaction. Further, the compound B may be a polymer having a functional group having reactivity with the reactive functional group X in the compound A in the main chain or side chain. In this case, compound A acts as a crosslinking agent.

In the polymer of the above (iii), in formulas (5a), (5b), and (5c), Z represents a bridged alicyclic skeleton, Y ¹ represents a single bond or a divalent organic group, and Y ² represents A single bond or a divalent organic group is shown, and Ra represents ^a hydrogen atom or a hydrocarbon group. A represents a group represented by the formula (a) or (b). In the formulas (a) and (b), R represents a monovalent organic group. In both formulas (a) and (b), the left side is the side that binds to Y ^1, and the right side is the side that binds to Y ² . The number of repeating units represented by formula (5a), (5b) or (5c) is, for example, about 5 to 25, preferably about 10 to 20.

The bridged alicyclic skeleton in Z, the divalent organic group in Y ¹ and Y ² , the hydrocarbon group in R ^a , and the monovalent organic group in R are the same as described above.

（式中、Ｚ、Ｙ¹、Ｒ^aは前記に同じ。ｑは２〜４の整数を示し、ｐは０〜２の整数を示す。ｐ＋ｑ＝２〜４である。）
で表されるホルミル基含有有橋脂環式化合物と、下記式（８）

（式中、Ｙ²は前記に同じ）
で表される多官能アミン化合物とを反応（重合）させた後、通常、生成ポリマーの末端のジアミノフェニル基を、ベンズアルデヒドなどのアルデヒド化合物と反応させてキャップをし、次いで、ＲＸ¹（Ｘ¹はハロゲン原子を示す。Ｒは前記に同じ）を反応させて、形成されたベンズイミダゾール環のＮＨ基の窒素原子にＲを導入することにより製造することができる。なお、ｐ＝２、ｑ＝２の場合は、式（５ａ）で表される化合物、ｐ＝１、ｑ＝３の場合は、式（５ｂ）で表される化合物、ｐ＝０、ｑ＝４の場合には、式（５ｃ）で表される化合物が得られる。 Of the polymers having repeating units represented by formulas (5a), (5b), and (5c), a polymer in which A is a group represented by formula (a) is represented by the following formula (7):

(In the formula, Z, Y ¹ and R ^a are the same as above. Q represents an integer of 2 to 4, p represents an integer of 0 to 2. p + q = 2 to 4)
A formyl group-containing bridged alicyclic compound represented by formula (8):

(Where Y ² is the same as above)
After the reaction (polymerization) with the polyfunctional amine compound represented by general formula (1), the diaminophenyl group at the end of the produced polymer is usually capped with an aldehyde compound such as benzaldehyde to cap it, and then RX ¹ (X ¹ Represents a halogen atom, and R is the same as described above, and can be produced by introducing R into the nitrogen atom of the NH group of the formed benzimidazole ring. In addition, when p = 2 and q = 2, the compound represented by Formula (5a), when p = 1 and q = 3, the compound represented by Formula (5b), p = 0, q = In the case of 4, the compound represented by the formula (5c) is obtained.

（式中、Ｚ、Ｙ¹、Ｒ^aは前記に同じ。ｑは２〜４の整数を示し、ｐは０〜２の整数を示す。ｐ＋ｑ＝２〜４である。）
で表されるアミノ基含有有橋脂環式化合物と、下記式（１０）

（式中、Ｙ²は前記に同じ）
で表される多官能アルデヒド化合物とを反応（重合）させた後、通常、生成ポリマーの末端のホルミル基を、ｏ−ジアミノベンゼンなどの隣接する炭素原子に２つのアミノ基が結合したジアミン化合物と反応させてキャップをし、次いで、ＲＸ¹（Ｘ¹はハロゲン原子を示す。Ｒは前記に同じ）を反応させて、形成されたベンズイミダゾール環のＮＨ基の窒素原子にＲを導入することにより製造することができる。なお、ｐ＝２、ｑ＝２の場合は、式（５ａ）で表される繰り返し単位を有する重合体、ｐ＝１、ｑ＝３の場合は、式（５ｂ）で表される繰り返し単位を有する重合体、ｐ＝０、ｑ＝４の場合には、式（５ｃ）で表される繰り返し単位を有する重合体が生成する。 Of the polymers having repeating units represented by formulas (5a), (5b), and (5c), a polymer in which A is a group represented by formula (b) is represented by the following formula (9).

(In the formula, Z, Y ¹ and R ^a are the same as above. Q represents an integer of 2 to 4, p represents an integer of 0 to 2. p + q = 2 to 4)
An amino group-containing Aribashi alicyclic compound represented by formula (10):

(Where Y ² is the same as above)
After the reaction (polymerization) with the polyfunctional aldehyde compound represented by the formula (1), a diamine compound in which two amino groups are bonded to an adjacent carbon atom, such as o-diaminobenzene, is usually used. By reacting and capping, then reacting RX ¹ (X ¹ is a halogen atom, R is the same as above) and introducing R into the nitrogen atom of the NH group of the benzimidazole ring formed. Can be manufactured. In addition, when p = 2 and q = 2, a polymer having a repeating unit represented by the formula (5a), and when p = 1 and q = 3, a repeating unit represented by the formula (5b) is used. In the case of the polymer having p = 0 and q = 4, a polymer having a repeating unit represented by the formula (5c) is formed.

Reaction of formyl group-containing bridged alicyclic compound represented by formula (7) with polyfunctional amine compound represented by formula (8), amino group-containing bridged alicyclic represented by formula (9) The reaction between the compound and the polyfunctional aldehyde compound represented by the formula (10) and the reaction for capping the end are carried out by using a solvent [for example, N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone, etc. Amides; cyclic aminoacetals such as dimethylimidazolidine and dimethylimidazolidinone (dimethylimidazolidine-dione)] in an oxygen atmosphere at a temperature of about −30 ° C. to 150 ° C. The so-called alkylation reaction using RX ¹ can be performed in the presence of a base such as sodium hydride at a temperature of about −20 ° C. to 120 ° C. in a solvent (for example, the solvent exemplified above). The reason for capping the polymer end is to make the end of the polymer hydrophobic to lower the hygroscopicity.

  The film-forming material of the present invention includes (i) a film-forming material prepared by dissolving an N-substituted benzimidazole ring-containing bridged alicyclic compound represented by formula (1) in a solvent, (ii) the compound A [ A N-substituted benzimidazole ring-containing bridged alicyclic compound represented by the formula (1), wherein k is 1 or 2, and a film-forming material obtained by dissolving the compound B in a solvent; iii) A film-forming material in which the N-substituted benzimidazole ring-containing polymer is dissolved in a solvent is included. Each of the above components dissolved in the solvent may be one type or two or more types.

  In the above (ii), when the reactive functional group X in the compound A is an ethynyl group which may have a substituent, the compound B is an ethynyl which may have a substituent in the molecule. A compound having two or more (for example, 2 to 4) groups (such as an ethynyl group optionally having the above-described substituent) can be used. Examples of such compounds include 1,3,5,7-tetrakis (4-phenylacetylene) adamantane, 1,3,5-tris (4-phenylacetylene) adamantane, 1,3,5-tris (4- And compounds having two or more ethynyl groups (acetylene groups) such as phenylacetylene) benzene. In addition, examples of the compound B include a polymer containing an ethynyl group which may have a substituent in the main chain or side chain. In the insulating film forming material containing the compound A containing the ethynyl group and such an ethynyl group-containing polymer, the compound A containing the ethynyl group functions as a crosslinking agent. For example, when an insulating film forming material (chemical solution) containing the compound A containing an ethynyl group and an ethynyl group-containing polymer is applied to a substrate and then heated from room temperature to 600 ° C., preferably 400 ° C., the crosslinking reaction proceeds. Thus, a film having a crosslinked structure and high heat resistance and mechanical strength can be obtained. The compound A containing an ethynyl group and other ethynyl group-containing compounds can be used alone or in combination of two or more.

  Examples of the solvent include organic solvents such as amides such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methyl-2-pyrrolidone; dimethylimidazolidine, dimethylimidazolidinone (dimethylimidazolidine-dione) Cyclic aminoacetals such as sulfoxides such as dimethyl sulfoxide; sulfones; nitriles such as acetonitrile, propionitrile, and benzonitrile; ketones such as acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone Esters such as formate ester, acetate ester, propionate ester, benzoate ester, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate (PGMEA); Ethers such as sun, tetrahydrofuran, diethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether (PGME); alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol; dichloromethane, Halogenated hydrocarbons such as dichloroethane, chloroform, carbon tetrachloride and chlorobenzene; nitro compounds such as nitromethane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and mesitylene; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; Aliphatic hydrocarbons such as hexane, heptane, and octane; and mixed solvents thereof.

  The film forming material of the present invention may contain other components as necessary. Examples of such components include the raw material components used for the synthesis of the respective dissolved components. Further, as another additive component, a catalyst for promoting polymerization, cyclization reaction, or the like can be used. Typical examples of the catalyst include acid catalysts such as sulfuric acid, methanesulfonic acid, and p-toluenesulfonic acid, and base catalysts. The amount of catalyst used is N-substituted benzimidazole ring-containing bridged alicyclic compound represented by formula (1) [in the case of (i)], compound A and compound B [in the case of (ii)], or N -It is 0-10 mol% with respect to a substituted benzimidazole ring containing polymer [in the case of (iii)], Preferably it is about 0-5 mol%.

  In order to improve applicability, a thickener that increases the viscosity of the solution may be added to the film forming material of the present invention. Typical examples of the thickener include alkylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol, and polyethylene glycol, and polyalkylene glycols. The usage-amount of a thickener is 0-20 weight% with respect to the whole film forming material, for example, Preferably it is about 0-10 weight%.

  You may add the adhesion promoter for improving the board | substrate adhesiveness of the film formed on a board | substrate to the film forming material of this invention. Typical examples of the adhesion promoter include trimethoxyvinylsilane, hexamethyldisilazane, γ-aminopropyltriethoxysilane, aluminum monoethylacetoacetate diisopropylate, and the like. The amount of the adhesion promoter used is the N-substituted benzimidazole ring-containing bridged alicyclic compound represented by formula (1) constituting the film forming material [in the case of (i)], compound A and compound B [( In the case of ii)] or N-substituted benzimidazole ring-containing polymer [in the case of (iii)], for example, 0 to 10% by weight, preferably about 0 to 5% by weight.

  The dissolution of each component in the organic solvent may be performed, for example, in an air atmosphere to the extent that each component or the like is not oxidized, but is preferably performed in an inert gas atmosphere such as nitrogen or argon. The temperature at which each component or the like is dissolved is not particularly limited, and may be heated according to the solubility and stability of each dissolved component, the boiling point of the solvent, and the like, for example, 0 to 200 ° C., preferably 10 to 150. It is about ℃.

  N-substituted benzimidazole ring-containing bridged alicyclic compound represented by formula (1) in the film-forming material [in the case of (i)], compound A and compound B [in the case of (ii)], or N— The concentration (total concentration) of the substituted benzimidazole ring-containing polymer [in the case of (iii)] can be appropriately selected in consideration of the solubility, coatability, workability, etc. of each dissolved component, for example, 5 to 70% by weight, Preferably, it is about 10 to 60% by weight.

  The thin film of the present invention (thin film having a pore structure) is obtained, for example, by applying the film forming material as a coating liquid on a substrate and then drying or heating. More specifically, it can be obtained, for example, by volatilizing the solvent by heating (firing) or the like, and by further causing polymerization or cyclization reaction. Examples of the base material include a silicon wafer, a metal substrate, and a ceramic substrate. The application method is not particularly limited, and conventional methods such as spin coating, dip coating, and spraying can be used.

  The heating temperature is not particularly limited as long as it is a temperature at which the solvent volatilizes or a temperature at which the monomer component can be converted into a polymer, but is generally 25 to 500 ° C. (eg 100 to 500 ° C.), preferably 25 to 450 ° C. ( For example, it is about 150-450 degreeC. Heating may be performed at a constant temperature or a stepped temperature gradient. The heating operation may be performed, for example, in an air atmosphere as long as the performance of the thin film to be formed is not affected, but is preferably performed in an inert gas (nitrogen, argon, etc.) atmosphere or a vacuum atmosphere.

  Upon heating, the solvent is volatilized, and further, a monomer component (compound [(N-substituted benzimidazole ring-containing bridged alicyclic compound represented by formula (1)] wherein X is a self-reactive functional group [( In the case of i)], the compound A and the compound B [in the case of (ii)]) are polymerized to form a polymer (polymer).

  In the present invention, for example, a tetrafunctional compound [for example, a compound in which n = 4 and m = 0 in formula (1) is used as a monomer component [including the compound represented by the above formula (7) or formula (9)] In the formula (7) or (9), a compound in which q = 4 and p = 0] is used, a structure in which a central skeleton (for example, an adamantane skeleton) is crossed in four directions as a vertex (crosslinking point) A network-like polymer film having (a unit in which three hexagons share two sides with each other) and a large number of holes can be formed. A trifunctional compound [for example, a compound in which n = 3 and m = 1 in the formula (1), a compound in which q = 3 and p = 1 in the formula (7) or (9)] was used as the monomer component. In some cases, it has a structure (unit consisting of three hexagons sharing two vertices or two sides) with a central skeleton (for example, adamantane skeleton) as a vertex (cross-linking point) in three directions, and a large number of holes A highly cross-linked polymer film having is formed. A bifunctional compound [for example, a compound in which n = 2 and m = 2 in formula (1), a compound in which q = 2 and p = 2 in formula (7) or (9)] was used as the monomer component. In some cases, the exclusion volume effect between the segments in the polymer molecular chain restricts the penetration of other molecular chains into the region where one polymer molecule exists, so that a high molecular weight polymer is obtained directly from the monomer mixture. A polymer film having a high porosity with a sparse packing structure can be formed.

  Further, when a tetrafunctional compound or a trifunctional compound and a bifunctional compound are used in combination as a monomer component, a large void is formed with a long distance (side) between adjacent cross-linking points (or nodal points). As a result, a very low dielectric constant can be achieved. More specifically, the tetrafunctional compound forms a crosslinking point having a three-dimensional structure branched in four directions, and the trifunctional compound forms a crosslinking point having a three-dimensional structure branched in three directions. / Or a trifunctional compound and a bifunctional compound can combine to produce a polymer having a sparse pore structure. In addition, when tetrafunctional compound (trifunctional compound) is used alone, many crosslink points are formed at the time of polymerization, so the density is increased, and the degree of molecular freedom is reduced, resulting in uncrosslinked points and increasing the dielectric constant. There is. For this reason, when a tetrafunctional compound and a trifunctional compound are used in combination, a steric hindrance occurs, and a void formed by a polymerization reaction due to a bond with the bifunctional compound is large. This is advantageous in that the polymer has a pore structure.

  In addition, when two kinds of tri- or tetra-functional compounds having functional groups that react with each other are used as monomer components, the density can be prevented from decreasing during the polymerization reaction due to steric hindrance between the monomer components. A polymer having a pore structure of can be obtained. That is, the tri- or tetrafunctional compound used for the monomer component is a tetrahedron (substantially regular tetrahedron) centered on a central skeleton (for example, adamantane skeleton), and the center part of the regular tetrahedron (for example, the central part of the adamantane skeleton). ) To the terminal functional group, it has a bulky part introduced by N-alkylation of the benzimidazole ring, thus preventing the penetration of other monomers into the space of the tetrahedral structure, and Invasion of oligomers, polymers, etc. is also limited. For this reason, the tetrahedral structure inherent to both monomer components is maintained, and a polymer having a low density structure in which pores having a size corresponding to the volume of these tetrahedra are regularly arranged can be formed. Furthermore, since the site introduced into the monomer molecule by N-alkylation of the benzimidazole ring is low in polarity, the intrinsic dielectric constant is low (about 2.0), and it plays the role of lowering the dielectric constant of the film. Yes.

  Since the polymer thin film formed in this way has a large number of molecular-level pores uniformly dispersed therein, the porosity is high and therefore the relative dielectric constant is low. Moreover, it has the advantage that it has sufficient heat resistance and mechanical strength due to cross-linking and has very little copper diffusion from the wiring. In particular, the N-substituted benzimidazole ring-containing polymer of the present invention has a bridged alicyclic skeleton as a central skeleton and a structural unit having an N-substituted benzimidazole ring as a repeating unit. The substituent bonded to the nitrogen atom not only reduces the polarity, but also makes it difficult for a low-molecular compound or the like to approach the central skeleton, so that the hygroscopicity and relative dielectric constant of the thin film can be extremely reduced.

  The thickness of the thin film formed by heating can be appropriately set depending on the application, but is generally 50 nm or more (about 50 to 2000 nm), preferably 100 nm or more (about 100 to 2000 nm), more preferably 300 nm or more (300 to About 2000 nm). If the film thickness is less than 50 nm, problems such as adverse effects on electrical characteristics such as the occurrence of leakage current, and difficulty in planarizing the film by chemical mechanical polishing (CMP) in the semiconductor manufacturing process are likely to occur. Particularly, it is not suitable for use as an interlayer insulating film.

  Since the thin film of the present invention exhibits a low dielectric constant and high heat resistance, it can be used, for example, as an insulating film in electronic material parts such as semiconductor devices, and is particularly useful as an interlayer insulating film.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. The film thickness of the polymer film was measured using an ellipsometer. The relative dielectric constant of the polymer film was measured by forming an Al electrode on the surface of the film. Infrared absorption spectrum was measured using a thin film transmission method.

Production Example 1

In a reaction vessel (three-necked flask), 77.68 g (0.362 mol) of 3,3′-diaminobenzidine represented by the above formula (B) was added, and 307 g of N, N-dimethylacetamide (DMAc) was added and dissolved. After that, it was kept at 0 ° C. or lower with an ice bath. A solution prepared by dissolving 10.1 g (0.018 mol) of adamantanetetrakisbenzaldehyde represented by the above formula (A) in 501 g of DMAc was dropped into this reaction vessel at a rate of 6 ml / min using a dropping funnel. During dropping, care was taken that the liquid temperature in the reaction solution did not exceed 0 ° C. After completion of the dropping, the dropping funnel was washed with 105 g of DMAc, and this was also dropped into the reaction vessel. The reaction vessel was heated by an oil bath while introducing a mixed gas of oxygen and nitrogen having an oxygen concentration of 5 mol% using a Teflon (registered trademark) tube, and the reaction temperature was kept at 90 ° C. for 9 hours. . After completion of the reaction, the reaction solution was added dropwise to 9.13 kg of water in another container, and a slurry consisting of a precipitate and a supernatant was stirred for about 1 hour after the completion of the addition. During the stirring, the reaction solution was bubbled with nitrogen to prevent amine oxidation. The produced precipitate was separated by filtration, transferred again to the reaction vessel, 1.83 kg of water was added, and the mixture was heated and refluxed for 30 minutes in a nitrogen atmosphere and washed with hot water. After the temperature was not lowered, the precipitate was filtered off, and the obtained filtrate was dried with a vacuum dryer.
After completion of drying, the obtained precipitate was transferred to a reaction vessel equipped with a reflux tube, tetrahydrofuran (THF) 1.83 kg was added, and the mixture was heated under reflux in a nitrogen atmosphere, and washed with THF. The solid content was again filtered, and the NMR spectrum and infrared absorption spectrum of the product dried by a vacuum dryer were measured. The NMR spectrum data shown in FIG. 1 and the infrared absorption spectrum data shown in FIG. It was confirmed that an amino group-containing adamantane derivative represented by (C) was formed. The yield of the amino group-containing adamantane derivative was 24.5 g, and the yield was 90%.
[NMR spectral data]
¹ H-NMR (DMSO-d6) δ (ppm): 2.32 (12H <—CH ₂ —>), 4.60 (16H <—NH ₂ >), 6.62-6.97 (12H <fragrance) Ring proton>), 7.53-7.78 (12H <aromatic ring proton>), 7.87 (8H), 8.24 (8H), 12.85 (4H)
[Infrared absorption spectrum data (cm ⁻¹ )]
3419 (N—H <stretching vibration>), 2933 (—CH ₂ —C—H <stretching vibration>), 1623 (—C═N— <stretching vibration>), 1420-1520 (aromatic ring <in-plane vibration) >), 1280 (aromatic-NH ₂ <stretching vibration>)

Production Example 2

Into a 100 mL two-necked eggplant flask, 6 g (4.5 mmol) of an amino group-containing adamantane derivative represented by the formula (C) is added, 100 g of N, N-dimethylacetamide (DMAc) is added, and the mixture is stirred for 10 minutes at room temperature in a nitrogen atmosphere. Stir. To this solution, 2.0 g (19 mmol) of benzaldehyde represented by the formula (D) was added dropwise. The mixture was heated to 100 ° C. and stirred for 13 hours while air bubbling the solution. The reaction mixture was dropped into 500 mL of water and filtered to obtain 6.5 g of an adamantane derivative (end-capped compound) represented by the solid formula (E). The yield was 86%.
[NMR spectral data]
¹ H-NMR (DMSO-d6) δ (ppm): 2.1-2.4 (12H), 7.4-8.4 (60H), 13.0 (8H)

Example 1

In a 50 mL two-necked eggplant flask, 0.48 g (20.0 mmol) of sodium hydride was placed, and 10 g of N, N-dimethylacetamide (DMAc) was added at 0 ° C. in a nitrogen atmosphere. 1.5 g (0.9 mmol) of the solid represented by the formula (E) was dissolved in 15 g of DMAc, put in a dropping funnel, dropped into the eggplant flask at 0 ° C., and stirred as it was for 30 minutes. 4-phenyl butyl chloride 3.3g (20.0mmol) represented by Formula (F) was dripped, and it stirred at 60 degreeC for 10 hours. The reaction mixture was added dropwise to 200 mL of methanol, and the solution was filtered to obtain 2.2 g of an N-substituted benzimidazole ring-containing bridged alicyclic compound represented by the solid formula (G). The yield was 90%.
[NMR spectral data]
¹ H-NMR (DMSO-d6) δ (ppm): 1.2 (16H), 1.5 (16H), 1.7 (16H), 2.2-2.5 (12H), 4.4 ( 16H), 6.8-8.0 (100H)

Production Example 3

A solution prepared by dissolving 2.08 g of 4-ethynylbenzaldehyde represented by (H) above in 20 g of N, N-dimethylacetamide (DMAc) was placed in a reaction vessel (three-necked flask). A solution prepared by dissolving 2.65 g of the amino group-containing adamantane derivative represented by (C) in 25 g of DMAc was dropped using a dropping funnel. After completion of dropping, the dropping funnel was washed with 10 g of DMAc, and this was also dropped into the reaction vessel. The reaction vessel was heated with an oil bath while maintaining the liquid temperature at 80 ° C. while introducing a mixed gas of oxygen / nitrogen having an oxygen concentration of 5 mol% using a Teflon (registered trademark) tube, and the reaction was continued for 7 hours. . After completion of the reaction, the reaction solution was added dropwise to 800 g of water in another container, and a slurry consisting of a precipitate and a supernatant was stirred for about 1 hour after the completion of the addition. The produced precipitate was separated by filtration, transferred again to the reaction vessel, added with 400 g of methanol, and stirred for 1 hour. After the precipitate was filtered off, the obtained filtrate was dried with a vacuum dryer. After completion of drying, the resulting precipitate was dissolved in DMAc 50 g and added dropwise to methanol 400 g. The precipitate was filtered off and dried with a vacuum dryer. The NMR spectrum and infrared absorption spectrum of the product were measured, and it was confirmed that the ethynyl group-containing adamantane derivative represented by the above formula (I) was formed. The yield of the ethynyl group-containing adamantane derivative was 3.09 g, and the yield was 87%.
[NMR spectral data]
¹ H-NMR (DMSO-d6) δ (ppm): 2.32 (12H <adamantane-CH _2- >), 4.38 (4H <ethynyl C—H>), 7.54-8.26 (6H <Aromatic ring CH>), 13.05 (4H <imidazole NH)
[Infrared absorption spectrum data (cm ⁻¹ )]
3422 (N—H <stretching vibration>), 2930 (—CH ₂ —CH—stretching vibration>), 2220 (ethynyl group <stretching vibration>, 1620 (—C═N— <stretching vibration>)), 1420-1520 (aromatic ring <in-plane vibration>), 1280 (aromatic-N-H <stretching vibration>), 809 (C-H <out-of-plane variable vibration>

Example 2

In a 50 mL two-necked eggplant flask, 0.48 g (20.0 mmol) of sodium hydride was placed, and 10 g of N, N-dimethylacetamide (DMAc) was added at 0 ° C. in a nitrogen atmosphere. 1.6 g (0.9 mmol) of an ethynyl group-containing adamantane derivative represented by the formula (I) was dissolved in 15 g of DMAc, put into a dropping funnel, dropped into an eggplant flask at 0 ° C., and stirred as it was for 30 minutes. 2.6 g (20.2 mmol) of benzyl chloride represented by the formula (J) was added dropwise and stirred at 60 ° C. for 5 hours. The reaction mixture was added dropwise to 200 mL of water, and the solution was filtered to obtain 2.0 g of an N-substituted benzimidazole ring-containing bridged alicyclic compound represented by the solid formula (K). The yield was 90%.
[NMR spectral data]
¹ H-NMR (CDCl ₃ ) δ (ppm): 2.1-2.3 (12H), 3.2 (4H), 5.5 (16H), 7.1-8.1 (96H)

Example 3

In a 50 mL two-necked eggplant flask, 0.48 g (20.0 mmol) of sodium hydride was placed, and 10 g of N, N-dimethylacetamide (DMAc) was added at 0 ° C. in a nitrogen atmosphere. 1.5 g (0.9 mmol) of the ethynyl group-containing adamantane derivative represented by the formula (I) was dissolved in 15 g of DMAc, put in a dropping funnel, dropped into the eggplant flask at 0 ° C., and stirred as it was for 30 minutes. 4-phenylbutyl chloride 3.3g (20.2mmol) represented by Formula (F) was dripped, and it stirred at 100 degreeC for 10 hours. The reaction mixture was added dropwise to 200 mL of water, and the precipitate was filtered to obtain 2.5 g of an N-substituted benzimidazole ring-containing bridged alicyclic compound represented by the solid formula (L). The yield was 85%.
[NMR spectral data]
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.6 (16H), 1.8 (16H), 2.2-2.5 (12H), 2.6 (16H), 3.2 (4H ), 4.3 (16H), 6.8-8.0 (96H)

Production Example 4

  In a reaction vessel (three-necked flask), 3.54 g (16.1 mmol) of 3,3′-diaminobenzidine represented by the above formula (B) is added, and 32 g of N, N-dimethylacetamide (DMAc) is added and dissolved. After that, the solution was kept at 0 ° C. or lower in an ice bath while blowing air into the solution using a Teflon (registered trademark) tube. To this reaction vessel, a solution obtained by dissolving 10.1 g (1.6 mmol) of adamantanetetrakisbenzaldehyde represented by the above formula (A) in 33 g of DMAc was added using a dropping funnel, and the liquid temperature in the reaction vessel was 0 ° C. It was dripped over 1 hour so that it might not exceed. After completion of the dropwise addition, the temperature of the oil bath was set to 90 ° C., and the reaction was performed for 6 hours with stirring. After completion of the reaction, the reaction solution was added dropwise to 500 g of water, and a slurry consisting of a precipitate and a supernatant was stirred for about 1 hour after the completion of the addition. In order to prevent oxidation of the amine, nitrogen gas was bubbled through the stirring liquid. The precipitate was separated by filtration, transferred again to the reaction vessel, 1.83 kg of water was added, heated under reflux in a nitrogen atmosphere for 30 minutes, and washed with hot water. The precipitate was filtered off before the temperature fell, and then dried by a vacuum dryer, to obtain 2.1 g of a polymer (precursor polymer) represented by the formula (M) having a weight average molecular weight of 22000. In the formula, n1 represents a positive integer (the number of repeating units) (hereinafter the same).

Production Example 5

In a 100 mL two-necked eggplant flask, 2 g of the polymer (precursor polymer) represented by the formula (M) was added, 100 g of N, N-dimethylacetamide (DMAc) was added, and the mixture was stirred at room temperature for 10 minutes in a nitrogen atmosphere. To this solution, 2.0 g (19 mmol) of benzaldehyde represented by the formula (D) was added dropwise. The mixture was heated to 100 ° C. and stirred for 13 hours while bubbling air through the solution. The reaction mixture was added dropwise to 500 mL of water, and the precipitate was filtered and dried under vacuum. As a result, 1.9 g (yield 90%) of an end-capped polymer solid represented by the formula (N) was obtained.
[NMR spectral data]
¹ H-NMR (DMSO-d6) δ (ppm): 2.1-2.4 (12H), 7.4-8.4 (60H), 13.0 (8H)

Example 4

In a 50 mL two-necked eggplant flask, 0.48 g (20.0 mmol) of sodium hydride was placed, and 10 g of N, N-dimethylacetamide (DMAc) was added at 0 ° C. in a nitrogen atmosphere. After dissolving 1.5 g (0.9 mmol) of the end-capped polymer represented by the formula (N) in 15 g of DMAc, it was placed in a dropping funnel, dropped into the eggplant flask at 0 ° C., and stirred as it was for 30 minutes. 2.6 g (20.2 mmol) of benzyl chloride represented by the formula (J) was added dropwise and stirred at 60 ° C. for 10 hours. The reaction mixture was added dropwise to 200 mL of methanol, and the solution was filtered to obtain 2.0 g of an N-substituted benzimidazole ring-containing bridged alicyclic compound represented by the solid formula (O). The yield was 90%.
[NMR spectral data]
¹ H-NMR (DMSO-d6) δ (ppm): 1.2 (16H), 1.5 (16H), 1.7 (16H), 2.2-2.5 (12H), 4.4 ( 16H), 6.8-8.0 (100H)

Production Example 6

To a 1000 mL four-necked flask, 9.6 g (72.0 mmol) of 4-ethynyl-1,2-diaminobenzene represented by the above formula (P) was added, and 50 g of N, N-dimethylacetamide (DMAc) was added. Then, using a Teflon (registered trademark) tube, the solution was kept at 25 ° C. while air was blown into the solution. A solution prepared by dissolving 5.0 g (9 mmol) of adamantanetetrakisbenzaldehyde represented by the above formula (A) in 100 g of DMAc was dropped into this mixed solution over 1.5 hours using a dropping funnel. After completion of dropping, the mixture was stirred at 25 ° C. for 1 hour, and then the reaction solution was heated to 80 ° C. and reacted for 24 hours with stirring. After completion of the reaction, the mixture was cooled to 25 ° C., 600 g of pure water was added dropwise, and a slurry consisting of a precipitate and a supernatant was stirred for about 1 hour after the completion of the addition. The produced precipitate was separated by filtration, transferred again to the reaction vessel, added with 600 g of methanol, and stirred for 1 hour. After the precipitate was filtered off, the obtained filtrate was dried with a vacuum dryer. After completion of drying, the resulting precipitate was dissolved in 150 g of DMAc, and 600 g of methanol was added dropwise thereto. After the precipitate was filtered off, the obtained filtrate was dried with a vacuum dryer. The ¹ H-NMR spectrum of the product was measured (see FIG. 3), and it was confirmed that an ethynyl group-containing adamantane derivative represented by the above formula (Q) was formed. The yield of the ethynyl group-containing adamantane derivative was 5.4 g, and the yield was 60%.
[NMR spectral data]
¹ H-NMR (DMSO-d6) δ (ppm): 2.1 (12H), 4.0-4.1 (4H), 7.2-8.2 (28H), 13.1 (4H)

Example 5

To a 100 mL four-necked flask, 0.4 g (16 mmol) of sodium hydride was added, and 10 g of N, N-dimethylacetamide (DMAc) was added at 25 ° C. under a nitrogen atmosphere. Thereto was added 2.0 g (16 mmol) of benzyl chloride represented by the above formula (J). 2 g (2 mmol) of an ethynyl group-containing adamantane derivative represented by the above formula (Q) was dissolved in 10 g of DMAc and then added to a dropping funnel, and dropped into the four-necked flask at 25 ° C. After completion of dropping, at 80 ° C. Stir for 6 hours. After completion of the reaction, the mixture was cooled to 25 ° C., and 10 g of methanol was added to the reaction solution. Thereafter, 50 g of pure water was added to precipitate a solid. The solid content was filtered off and dried in a vacuum dryer. The ¹ H-NMR spectrum of the product was measured (see FIG. 4), and it was confirmed that an N-substituted ethynylbenzimidazole ring-containing bridged alicyclic compound represented by the above formula (R) was formed. The yield of the N-substituted ethynylbenzimidazole ring-containing bridged alicyclic compound was 1.5 g, and the yield was 55%.
[NMR spectral data]
¹ H-NMR (CDCl ₃ ) δ (ppm): 2.2 (12H), 3.00 (4H), 5.45 (8H), 7.0-8.1 (60H)

Example 6

To a 100 mL four-necked flask, 0.4 g (16 mmol) of sodium hydride was added, and 10 g of N, N-dimethylacetamide (DMAc) was added at 25 ° C. under a nitrogen atmosphere. Thereto was added 2.7 g (16 mmol) of 4-phenylbutyl chloride represented by the above formula (F). 2 g (2 mmol) of an ethynyl group-containing adamantane derivative represented by the above formula (Q) was dissolved in 10 g of DMAc and then added to a dropping funnel, and dropped into the four-necked flask at 25 ° C. After completion of dropping, at 80 ° C. Stir for 6 hours. After completion of the reaction, the mixture was cooled to 25 ° C., and 10 g of methanol was added to the reaction solution. Thereafter, 50 g of pure water was added, and the oil was separated by decantation. Thereafter, it was dissolved again in 10 g of DMAc, and 10 g of methanol and 10 g of pure water were added to precipitate a solid content. The solid content was filtered off and dried in a vacuum dryer. The ¹ H-NMR spectrum of the product was measured (see FIG. 5), and it was confirmed that the N-substituted ethynylbenzimidazole ring-containing bridged alicyclic compound represented by the above formula (S) was formed. The yield of the N-substituted ethynylbenzimidazole ring-containing bridged alicyclic compound was 0.75 g, and the yield was 25%.
[NMR spectral data]
¹ H-NMR (CDCl ₃ ) δ (ppm): 1.17 (8H), 1.60 (8H), 1.88 (8H), 2.1 (12H), 2.94-3.1 (4H) ), 4.25 (8H), 7.2-8.2 (60H)

Example 7

In a 100 mL four-necked flask, 0.25 g (10 mmol) of sodium hydride was placed, and 20 g of N, N-dimethylacetamide (DMAc) was added at 25 ° C. under a nitrogen atmosphere. Thereto was added 3.2 g (10 mmol) of 1-bromodocosane represented by the above formula (T). 2 g (2 mmol) of an ethynyl group-containing adamantane derivative represented by the above formula (Q) is dissolved in 10 g of DMAc and then added to a dropping funnel, and dropped into the four-necked flask at 40 ° C. After completion of dropping, at 80 ° C. Stir for 8 hours. After completion of the reaction, the mixture was cooled to 25 ° C., and 80 g of methanol was added to the reaction solution. Thereafter, 160 g of hexane was added and stirred, followed by liquid separation, and the hexane layer was taken out. 100 g of pure water was added to the hexane layer, and the mixture was stirred and separated to remove the hexane layer again. The hexane layer was concentrated and purified by silica gel column chromatography using hexane as a developing solvent. The obtained hexane solution (eluent) was allowed to stand for 24 hours to precipitate a solid content. The precipitated solid was separated into solid and liquid by decantation and dried with a vacuum dryer. A ¹ H-NMR spectrum of the product was measured (see FIG. 6), and it was confirmed that an N-substituted ethynylbenzimidazole ring-containing bridged alicyclic compound represented by the above formula (U) was formed. The yield of the N-substituted ethynylbenzimidazole ring-containing bridged alicyclic compound was 1.0 g, and the yield was 22%.
[NMR spectral data]
¹ H-NMR (CDCl ₃ ) δ (ppm): 0.8 (12H), 1.2 (152H), 1.8 (8H), 2.3 (12H), 3.0-3.1 (4H) ), 4.2 (8H), 7.3-8.0 (28H)

Evaluation test 1
The adamantane derivative (end-capped compound) represented by the formula (E) obtained in Production Example 2 was mixed with DMAc and 1,3-dimethyl-2-imidazolidinone (DMI) (weight ratio 1: 1). A 10% by weight solution was prepared by dissolving in 2%. This solution was applied onto the wafer using a spin coater. The solvent was completely volatilized by heating the coated wafer in an electric furnace at 250 ° C. for 1 hour in a nitrogen atmosphere. When the electrical characteristics of the thin film thus obtained (film thickness: 250 nm) were examined, the relative dielectric constant was 3.4. Moreover, when the thin film was left in the air, the value of the current flowing due to moisture absorption of the thin film increased.
On the other hand, electrical properties of a thin film (film thickness: 200 nm) obtained by treating the N-substituted benzimidazole ring-containing bridged alicyclic compound represented by the formula (G) obtained in Example 1 in the same manner. As a result, no increase in current value due to the effect of moisture absorption was obtained. The relative dielectric constant was 3.0.

Evaluation test 2
The ethynyl group-containing adamantane derivative represented by the formula (I) obtained in Production Example 3 is dissolved in a mixture of DMAc and 1,3-dimethyl-2-imidazolidinone (DMI) (weight ratio 1: 1). A 10 wt% solution was prepared. This solution was applied onto the wafer using a spin coater. The coated wafer was heated in an electric furnace in a nitrogen atmosphere at 400 ° C. for 30 minutes to advance the crosslinking reaction. When the electrical characteristics of the thin film thus obtained (film thickness: 300 nm) were examined, the relative dielectric constant was 3.0. Moreover, when the thin film was left in the air, the value of the current flowing due to moisture absorption of the thin film increased.
On the other hand, the electrical properties of a thin film (film thickness: 220 nm) obtained by treating the N-substituted benzimidazole ring-containing bridged alicyclic compound represented by the formula (K) obtained in Example 2 in the same manner. As a result, no increase in current value due to the effect of moisture absorption was obtained. The relative dielectric constant was 3.0.
Moreover, the electrical property of the thin film (film thickness: 210 nm) obtained by processing similarly the N-substituted benzimidazole ring containing bridged alicyclic compound represented by Formula (L) obtained in Example 3 As a result, no increase in current value due to the effect of moisture absorption was obtained. The relative dielectric constant was 3.0.

Evaluation test 3
The end-capped polymer represented by the formula (N) obtained in Production Example 5 was dissolved in a mixed solution of DMAc and 1,3-dimethyl-2-imidazolidinone (DMI) (weight ratio 1: 1), A 10 wt% solution was prepared. This solution was applied onto the wafer using a spin coater. The solvent was completely volatilized by heating the coated wafer in an electric furnace at 250 ° C. for 1 hour in a nitrogen atmosphere. When the electrical characteristics of the thin film thus obtained (film thickness: 260 nm) were examined, the relative dielectric constant was 3.5. Moreover, when the thin film was left in the air, the value of the current flowing due to moisture absorption of the thin film increased.
On the other hand, the electrical properties of a thin film (film thickness: 280 nm) obtained by treating the N-substituted benzimidazole ring-containing bridged alicyclic compound represented by the formula (O) obtained in Example 4 in the same manner. As a result, no increase in current value due to the effect of moisture absorption was obtained. The relative dielectric constant was 3.0.

Evaluation test 4
The ethynyl group-containing adamantane derivative represented by the formula (Q) obtained in Production Example 6 is dissolved in a mixed solution of DMAc and 1,3-dimethyl-2-imidazolidinone (DMI) (weight ratio 1: 1). A 10 wt% solution was prepared. This solution was applied onto the wafer using a spin coater. The coated wafer was heated in an electric furnace in a nitrogen atmosphere at 350 ° C. for 1 hour to advance the crosslinking reaction. When the electrical characteristics of the thin film thus obtained (film thickness: 300 nm) were examined, the relative dielectric constant was 3.1. Even when the thin film was left in the air, no increase in current value due to moisture absorption of the thin film was observed.
The N-substituted benzimidazole ring-containing bridged alicyclic compound represented by the formula (R) obtained in Example 5 was dissolved in cyclohexanone to prepare a 10% by weight solution. This solution was applied onto the wafer using a spin coater. The coated wafer was heated in an electric furnace in a nitrogen atmosphere at 350 ° C. for 1 hour to advance the crosslinking reaction. When the electrical characteristics of the thin film thus obtained (film thickness: 460 nm) were examined, the relative dielectric constant was 3.0. Even when the thin film was left in the air, no increase in current value due to moisture absorption of the thin film was observed.
The N-substituted benzimidazole ring-containing bridged alicyclic compound represented by the formula (S) obtained in Example 6 was dissolved in cyclohexanone to prepare a 10% by weight solution. This solution was applied onto the wafer using a spin coater. The coated wafer was heated in an electric furnace in a nitrogen atmosphere at 350 ° C. for 1 hour to advance the crosslinking reaction. When the electrical characteristics of the thin film thus obtained (film thickness: 400 nm) were examined, the relative dielectric constant was 3.0. Even when the thin film was left in the air, no increase in current value due to moisture absorption of the thin film was observed.
The N-substituted benzimidazole ring-containing bridged alicyclic compound represented by the formula (U) obtained in Example 7 was dissolved in cyclohexanone to prepare a 7% by weight solution. This solution was applied onto the wafer using a spin coater. The coated wafer was heated in an electric furnace in a nitrogen atmosphere at 300 ° C. for 1 hour to advance the crosslinking reaction. When the electrical characteristics of the thin film thus obtained (film thickness: 310 nm) were examined, the relative dielectric constant was 2.6. Even when the thin film was left in the air, no increase in current value due to moisture absorption of the thin film was observed.
Leakage current of the thin film formed from the ethynyl group-containing adamantane derivative obtained in Production Example 6 and the thin film formed from the N-substituted ethynylbenzimidazole ring-containing bridged alicyclic compound obtained in Examples 5 to 7 The characteristics are shown in FIG. The horizontal axis in FIG. 7 is the applied electric field strength (V / cm), and the vertical axis is the leakage current density (A / cm ² ). The leakage current characteristics were measured by a probe method.

2 is an NMR spectrum of an amino group-containing adamantane derivative obtained in Production Example 1. 2 is an infrared absorption spectrum of an amino group-containing adamantane derivative obtained in Production Example 1. 4 is an NMR spectrum of an ethynyl group-containing adamantane derivative obtained in Production Example 6. 2 is an NMR spectrum of the N-substituted ethynylbenzimidazole ring-containing bridged alicyclic compound obtained in Example 5. 2 is an NMR spectrum of the N-substituted ethynylbenzimidazole ring-containing bridged alicyclic compound obtained in Example 6. 2 is an NMR spectrum of the N-substituted ethynylbenzimidazole ring-containing bridged alicyclic compound obtained in Example 7. Leakage current of the thin film formed by the ethynyl group-containing adamantane derivative obtained in Production Example 6 and the thin film formed by the N-substituted ethynylbenzimidazole ring-containing bridged alicyclic compound obtained in Examples 5 to 7 It is a graph which shows a characteristic.

Claims (7)

The following formula (1 ' )

(In the formula, Z represents an adamantane-1,3,5,7-tetrayl group , Y ¹ represents a single bond or an arylene group , and Y ² represents a single bond or the following formula:

(Wherein R ² represents a divalent aliphatic hydrocarbon group having 1 to 50 carbon atoms. R ′ represents a hydrogen atom or the following formula:

(In the formula, R ¹ represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 50 carbon atoms. J represents an integer of 0 to 3)
Represents a group selected from: In each formula, the right and left direction of the bond does not matter)
Or a divalent group in which two or more of these are bonded , and X is a hydrogen atom , an alkyl group having 1 to 10 carbon atoms , an aryl group having 6 to 20 carbon atoms , or a trialkylsilyl group. Represents an ethynyl group optionally having a substituent selected from R ^a represents a hydrogen atom or a hydrocarbon group. A is the following formula (a )

(Where R is the following formula

(In the formula, R ¹ represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 50 carbon atoms. J represents an integer of 0 to 3)
Represents a group selected from: In the formula (a), the left side is the side bonded to Y ^1, and the right side is the side bonded to Y ² )
The group represented by these is shown. n is 3 or 4 , m is 0 or 1 , and k is an integer of 0-2. n + m = 4 . And a plurality of Y ¹ , Y ² , A ¹ , R in the molecule and X in the case where there are a plurality thereof may be the same or different)
An N-substituted benzimidazole ring-containing bridged alicyclic compound represented by the formula: Claim 1 Symbol placement No N- substituted benzimidazole ring-containing bridged alicyclic compound [where, k in the formula (1 ') is 1 or 2, X is an alkyl group having 1 to 10 carbon atoms, carbon A ethynyl group optionally having a substituent selected from an aryl group of 6 to 20 and a trialkylsilyl group is represented]. N ′ having a weight average molecular weight of 200 to 100,000 obtained by polymerizing A ′ Substituted benzimidazole ring-containing polymer. The following formula ( 5b) or (5c)

[ Wherein Z represents an adamantane-1,3,5,7-tetrayl group , Y ¹ represents a single bond or an arylene group , and Y ² represents a single bond or the following formula:

(Wherein R ² represents a divalent aliphatic hydrocarbon group having 1 to 50 carbon atoms. R ′ represents a hydrogen atom or the following formula:

(In the formula, R ¹ represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 50 carbon atoms. J represents an integer of 0 to 3)
Represents a group selected from: In each formula, the right and left direction of the bond does not matter)
Or a divalent group in which two or more of these are bonded , and Ra represents ^a hydrogen atom or a hydrocarbon group. A is the following formula (a )

(Where R is the following formula

(In the formula, R ¹ represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 50 carbon atoms. J represents an integer of 0 to 3)
Represents a group selected from: In the formula (a), the left side is the side bonded to Y ^1, and the right side is the side bonded to Y ² )
Represents a group represented by
Have a in represented by the repeating unit, the weight average molecular weight is from 200 to 100,000 N-substituted benzimidazole ring-containing polymer. A film-forming material obtained by dissolving the N-substituted benzimidazole ring-containing bridged alicyclic compound according to claim 1 in a solvent. A film-forming material obtained by dissolving the N-substituted benzimidazole ring-containing polymer according to claim 2 or 3 in a solvent. A method for producing a thin film, wherein the film forming material according to claim 4 or 5 is applied onto a substrate and dried or reacted by heating to form a thin film. A thin film formed by the method for producing a thin film according to claim 6 .

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