JP2009019193A - Insulating film forming material, insulating film and producing method thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an insulating film forming material capable of forming an insulating film useful for the production of a semiconductor, having high heat resistance and a very low relative dielectric constant, and ensuring less variation in the relative dielectric constant. <P>SOLUTION: The insulating film forming material contains two compounds A and B capable of forming a polymer having a hole structure by a reaction between functional groups, wherein at least one of the compounds A and B has a bridged alicyclic skeleton or aromatic ring skeleton as a central skeleton, at least one has a heat resistant skeleton comprising an aromatic ring-containing divalent organic group between the central skeleton and the functional group, and at least one has a flexible unit comprising an organic group containing at least an alkylene group or an ether bond within a molecule and having a total number of atoms of 2-20. The functional group of the compound A and the functional group of the compound B are a pair of functional groups which react with each other to form a heterocycle, or both are groups each containing an ethynyl group which may have a substituent. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an insulating film for use in the production of a semiconductor, particularly an insulating film having excellent heat resistance and mechanical strength and exhibiting a low relative dielectric constant, a method for producing the same, a polymerizable compound useful for obtaining the insulating film, and an insulating film The present invention relates to a forming material and a polymer having a pore structure.

  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, the insulating film has a problem in that the dielectric constant tends to vary because many unreacted terminals remain. 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 form a polymer and an insulating film having a high heat resistance and an extremely low relative dielectric constant useful for manufacturing semiconductors, and having a pore structure with little variation in relative dielectric constant, and a method for manufacturing the same. Another object is to provide an insulating film forming material and a polymerizable compound.

  As a result of intensive studies to achieve the above object, the present inventors have two or more functional groups or functional groups that can be bonded to each other to form a heterocyclic ring, etc., and the functional groups or functional groups Two compounds capable of forming a polymer having a pore structure by a group reaction, at least one of which has a flexible unit of a specific structure is polymerized, or reacts with each other in the molecule to form a heterocycle, etc. A compound capable of forming a polymer having a pore structure by reaction of the functional group or functional group, and having a specific structure in the molecule. The inventors have found that when a compound having a flexible unit is polymerized, an insulating film having an extremely low relative dielectric constant and a small variation in relative dielectric constant can be efficiently obtained, and the present invention has been completed.

That is, the present invention has two or more functional groups or functional group groups in the molecule of each compound, and the functional group or functional group group of one compound and the functional group or functional group group of the other compound Having two or more functional groups or groups of functional groups in the molecule, and / or two compounds A and B that can be polymerized by bonding to form a polymer having a pore structure, and / or An insulating film forming material comprising a compound C capable of forming a polymer having a pore structure by polymerization by bonding of a functional group or a functional group with another functional group or a functional group, the compound A Provided is an insulating film forming material characterized in that the compound B and the compound C satisfy the following condition (i) or (ii).
(I) At least one of Compound A and Compound B has a bridged alicyclic skeleton or an aromatic ring skeleton as a central skeleton, and at least one of Compound A and Compound B is a central skeleton and the functional group or functional group group Having a heat-resistant skeleton composed of a divalent organic group containing an aromatic ring, and at least one of compound A and compound B having 2 to 20 atoms in total containing at least an alkylene group or an ether bond in the molecule A pair of functional groups or functional groups having a flexible unit composed of an organic group and capable of forming a heterocyclic ring by reacting the functional group or functional group group of compound A and the functional group or functional group group of compound B with each other. (Ii) Compound C has a bridged alicyclic skeleton or an aromatic ring skeleton as a central skeleton, and is a group that includes an ethynyl group that may have a substituent. Said one officer A heat-resistant skeleton composed of a divalent organic group containing an aromatic ring between the group or functional group and / or between the central skeleton and another functional group or functional group, A flexible unit comprising an organic group having 2 to 20 atoms in total containing at least an alkylene group or an ether bond between the functional group or the functional group of and / or between the central skeleton and another functional group or the functional group. And one functional group or functional group group of compound C and another functional group or functional group group are a pair of functional groups or functional groups capable of reacting with each other to form a heterocyclic ring, Or a group containing an ethynyl group which may have a substituent.

（式中、ｒは０〜５の整数を示す） In the insulating film forming material, the bridged alicyclic ring or aromatic ring related to the bridged alicyclic skeleton or aromatic ring skeleton as the central skeleton of compound A or compound B or compound C is selected from the following formulae: It is preferably a ring or a ring in which two or more of these are bonded.

(Wherein r represents an integer of 0 to 5)

（式中、ｓは０〜５の整数を示す） Further, the heat-resistant skeleton composed of a divalent organic group containing an aromatic ring included in at least one of Compound A and Compound B or Compound C is a group selected from the following formulas, or a group in which two or more of these are bonded. Is preferred.

(In the formula, s represents an integer of 0 to 5)

（式中、ｔは１〜１９の整数を示し、ｕは１〜１０の整数を示し、ｖは１〜３の整数を示し、ｗは１〜１６の整数を示し、ｘは１〜１４の整数を示す。ｙ及びｚは、それぞれ０〜６の整数を示す。但し、ｙ及びｚは同時に０となることはない） Moreover, the flexible unit consisting of an organic group having 2 to 20 atoms in total containing at least one of the compound A and the compound B or the alkylene group or ether bond of the compound C is a flexible unit comprising a group selected from the following formulae. Is preferred.

(In the formula, t represents an integer of 1 to 19, u represents an integer of 1 to 10, v represents an integer of 1 to 3, w represents an integer of 1 to 16, and x represents 1 to 14) Y and z are each an integer of 0 to 6, provided that y and z are not 0 at the same time.

  Furthermore, the functional group or functional group of compound A and the functional group or functional group of compound B react with each other to form a heterocyclic ring, or one functional group or functional group of compound C and another functional group or function. The heterocyclic ring formed by the group group reacting with each other is, for example, a benzimidazole ring, a benzoxazole ring, or a benzthiazole ring.

［式中、Ｘ¹は２〜４価の有橋脂環式基又は芳香族環式基を示す。Ｙ^1a、Ｙ^1bは、同一又は異なって、単結合、２価の芳香族炭化水素基、２価の芳香族複素環式基、２価の芳香族複素環式基の前駆体に相当する２価の基、又はこれらの基が２以上結合した２価の基を示す。Ｗ¹はアルキレン基又はエーテル結合を少なくとも含む全原子数２〜２０の２価の基からなるフレキシブルユニットを示す。Ｚ¹は下記式（２）におけるＺ²と反応して複素環を形成しうる官能基若しくは官能基群、又は置換基を有していてもよいエチニル基を含む基（但し、式（２）におけるＺ²が置換基を有していてもよいエチニル基を含む基である場合に限る）を示す。Ｒ¹は、水素原子又は炭化水素基を示す。ｎ１は２〜４の整数を示し、ｎ２は０〜２の整数を示す。ｎ１＋ｎ２＝２〜４である。分子内の複数のＹ^1a、Ｙ^1b、Ｗ¹、Ｚ¹、及び複数存在する場合のＲ¹は、それぞれ同一であっても異なっていてもよい］
で表される化合物、又は下記式（１ｂ）

［式中、Ｙ¹は、単結合、２価の芳香族炭化水素基、２価の芳香族複素環式基、２価の芳香族複素環式基の前駆体に相当する２価の基、又はこれらの基が２以上結合した２価の基を示す。Ｗはアルキレン基又はエーテル結合を少なくとも含む全原子数２〜２０の２〜４価の基からなるフレキシブルユニットを示す。Ｚ¹は下記式（２）におけるＺ²と反応して複素環を形成しうる官能基若しくは官能基群、又は置換基を有していてもよいエチニル基を含む基（但し、式（２）におけるＺ²が置換基を有していてもよいエチニル基を含む基である場合に限る）を示す。ｎは２〜４の整数を示す。分子内の複数のＹ¹、Ｚ¹はそれぞれ同一であっても異なっていてもよい］
で表される化合物であり、化合物Ｂが下記式（２）

［式中、Ｘ²は２〜４価の有橋脂環式基又は芳香族環式基を示す。Ｙ^2a、Ｙ^2bは、同一又は異なって、単結合、２価の芳香族炭化水素基、２価の芳香族複素環式基、２価の芳香族複素環式基の前駆体に相当する２価の基、又はこれらの基が２以上結合した２価の基を示す。Ｗ²はアルキレン基又はエーテル結合を少なくとも含む全原子数２〜２０の２価の基からなるフレキシブルユニットを示す。Ｚ²は前記式（１ａ）又は（１ｂ）におけるＺ¹と反応して複素環を形成しうる官能基若しくは官能基群、又は置換基を有していてもよいエチニル基を含む基（但し、式（１ａ）又は（１ｂ）におけるＺ¹が置換基を有していてもよいエチニル基を含む基である場合に限る）を示す。Ｒ²は、水素原子又は炭化水素基を示す。ｍ１は２〜４の整数を示し、ｍ２は０〜２の整数を示す。ｍ１＋ｍ２＝２〜４である。ｉは０又は１を示し、ｋは０又は１を示す。分子内の複数のＹ^2a、Ｙ^2b、Ｗ²、Ｚ²、及び複数存在する場合のＲ²は、それぞれ同一であっても異なっていてもよい］
で表される化合物である。 In the insulating film forming material, it is preferable that the compound A, the compound B, and the compound C satisfy the following condition (iii) or (iv).
(Iii) Compound A is represented by the following formula (1a)

[Wherein, X ¹ represents a divalent to tetravalent bridged alicyclic group or an aromatic cyclic group. Y ^1a and Y ^1b are the same or different and represent a single bond, a divalent aromatic hydrocarbon group, a divalent aromatic heterocyclic group, or a precursor of a divalent aromatic heterocyclic group. And a divalent group in which two or more of these groups are bonded. W ¹ represents a flexible unit composed of a divalent group having 2 to 20 atoms and containing at least an alkylene group or an ether bond. Z ¹ is a group containing a functional group or a functional group capable of reacting with Z ² in the following formula (2) to form a heterocyclic ring, or an ethynyl group optionally having a substituent (provided that the formula (2) In which Z ² is a group containing an ethynyl group which may have a substituent. R ¹ represents a hydrogen atom or a hydrocarbon group. n1 shows the integer of 2-4, n2 shows the integer of 0-2. n1 + n2 = 2-4. A plurality of Y ^1a , Y ^1b , W ¹ , Z ¹ in the molecule, and R ¹ in the case where a plurality exist may be the same or different.]
Or a compound represented by the following formula (1b)

[Wherein Y ¹ represents a single bond, a divalent aromatic hydrocarbon group, a divalent aromatic heterocyclic group, a divalent group corresponding to a precursor of a divalent aromatic heterocyclic group, Or the bivalent group which these groups couple | bonded two or more is shown. W represents a flexible unit composed of a divalent to tetravalent group having 2 to 20 atoms and containing at least an alkylene group or an ether bond. Z ¹ is a group containing a functional group or a functional group capable of reacting with Z ² in the following formula (2) to form a heterocyclic ring, or an ethynyl group optionally having a substituent (provided that the formula (2) In which Z ² is a group containing an ethynyl group which may have a substituent. n shows the integer of 2-4. Plural Y ¹ and Z ¹ in the molecule may be the same or different.
The compound B is represented by the following formula (2):

[Wherein, X ² represents a divalent to tetravalent bridged alicyclic group or an aromatic cyclic group. Y ^2a and Y ^2b are the same or different and represent a single bond, a divalent aromatic hydrocarbon group, a divalent aromatic heterocyclic group, or a precursor of a divalent aromatic heterocyclic group. And a divalent group in which two or more of these groups are bonded. W ² represents a flexible unit composed of a divalent group having 2 to 20 atoms in total containing at least an alkylene group or an ether bond. Z ² represents a functional group or a group of functional groups that can form a heterocyclic ring by reacting with Z ¹ in the formula (1a) or (1b), or a group containing an ethynyl group which may have a substituent (provided that Z ¹ in formula (1a) or (1b) is limited to a group containing an ethynyl group which may have a substituent. R ² represents a hydrogen atom or a hydrocarbon group. m1 represents an integer of 2 to 4, and m2 represents an integer of 0 to 2. m1 + m2 = 2-4. i represents 0 or 1, and k represents 0 or 1. A plurality of Y ^2a , Y ^2b , W ² , Z ² in the molecule, and R ² in the case where a plurality exist may be the same or different.]
It is a compound represented by these.

［式中、Ｘ¹は２〜４価の有橋脂環式基又は芳香族環式基を示す。Ｙ^1a、Ｙ^1b、Ｙ^2a、Ｙ^2bは、同一又は異なって、単結合、２価の芳香族炭化水素基、２価の芳香族複素環式基、２価の芳香族複素環式基の前駆体に相当する２価の基、又はこれらの基が２以上結合した２価の基を示す。Ｗ¹、Ｗ²は、同一又は異なって、アルキレン基又はエーテル結合を少なくとも含む全原子数２〜２０の２価の基からなるフレキシブルユニットを示す。Ｚ¹、Ｚ²は、互いに反応して複素環を形成しうる対となる官能基若しくは官能基群であるか、又はＺ¹、Ｚ²のいずれもが置換基を有していてもよいエチニル基を含む置換基を示す。Ｒ¹は、水素原子又は炭化水素基を示す。ｋは０又は１を示す。ｐ１、ｐ２は、それぞれ１〜３の整数を示し、ｐ３は０〜２の整数を示す。ｐ１＋ｐ２＋ｐ３＝２〜４である。分子内に複数存在する場合のＹ^1a、Ｙ^1b、Ｙ^2a、Ｙ^2b、Ｗ¹、Ｗ²、Ｚ¹、Ｚ²、Ｒ¹は、それぞれ同一であっても異なっていてもよい］
で表される化合物である。 (Iv) Compound C is represented by the following formula (3)

[Wherein, X ¹ represents a divalent to tetravalent bridged alicyclic group or an aromatic cyclic group. Y ^1a , Y ^1b , Y ^2a and Y ^2b are the same or different and are each a single bond, a divalent aromatic hydrocarbon group, a divalent aromatic heterocyclic group or a divalent aromatic heterocyclic group. A divalent group corresponding to a precursor or a divalent group in which two or more of these groups are bonded to each other is shown. W ¹ and W ² are the same or different and each represents a flexible unit comprising a divalent group having 2 to 20 atoms and containing at least an alkylene group or an ether bond. Z ¹ and Z ² are a functional group or a group of functional groups that can form a heterocycle by reacting with each other, or both Z ¹ and Z ² may have a substituent. A substituent containing a group is shown. R ¹ represents a hydrogen atom or a hydrocarbon group. k represents 0 or 1. p1 and p2 each represent an integer of 1 to 3, and p3 represents an integer of 0 to 2. p1 + p2 + p3 = 2-4. Y ^1a , Y ^1b , Y ^2a , Y ^2b , W ¹ , W ² , Z ¹ , Z ² , R ¹ in the case where there are a plurality in the molecule may be the same or different.
It is a compound represented by these.

X ¹ in the above formulas (1a) and (3) is, for example, a divalent to tetravalent aromatic or non-aromatic cyclic group.

（式中、ｒは０〜５の整数を示す） The aromatic or non-aromatic ring related to the divalent to tetravalent aromatic or non-aromatic cyclic group is preferably a ring selected from the following formula or a ring in which two or more of these are bonded.

(Wherein r represents an integer of 0 to 5)

（式中、ｓは０〜５の整数を示す） Y ^1a , Y ^1b , Y ¹ , Y ^2a , Y ^2b in the formula (1a), formula (1b), formula (2), and formula (3) are a single bond, a group selected from the following formulas, or these: Is preferably a group in which two or more are bonded.

(In the formula, s represents an integer of 0 to 5)

（式中、ｔは１〜１９の整数を示し、ｕは１〜１０の整数を示し、ｖは１〜３の整数を示し、ｗは１〜１６の整数を示し、ｘは１〜１４の整数を示す。ｙ及びｚは、それぞれ０〜６の整数を示す。但し、ｙ及びｚは同時に０となることはない） In the formula (1a), formula (1b), formula (2), and formula (3), W ¹ , W, and W ² are preferably flexible units composed of groups selected from the following formulas.

(In the formula, t represents an integer of 1 to 19, u represents an integer of 1 to 10, v represents an integer of 1 to 3, w represents an integer of 1 to 16, and x represents 1 to 14) Y and z are each an integer of 0 to 6, provided that y and z are not 0 at the same time.

Heterocycle formed by Z ¹ in Formula (1a) or Formula (1b) and Z ² in Formula (2), Complex formed by Z ¹ in Formula (3) and Z ² in Formula (3) The ring is, for example, a benzimidazole ring, a benzoxazole ring or a benzthiazole ring.

Z ¹ in formula (1a) or formula (1b) and Z ² in formula (2), or Z ¹ in formula (3) and Z ² in formula (3) are either a carboxyl group or a substituted oxycarbonyl group. Group, a formyl group, a haloformyl group or a group containing an optionally substituted ethynyl group, the other being a 3,4-diaminophenyl group, a 3-amino-4-hydroxyphenyl group, a 4-amino-3 -Hydroxyphenyl group, 3-amino-4-mercaptophenyl group, 4-amino-3-mercaptophenyl group or a group containing an optionally substituted ethynyl group (provided that one has a substituent) In the case where it is a group containing an ethynyl group which may be substituted, the other is also a group containing an ethynyl group which may have a substituent).

  The insulating film forming material includes a solution in which compound A and compound B and / or compound C are dissolved in an organic solvent.

  The present invention also provides a polymer having a pore structure obtained by subjecting the insulating film forming material to a polymerization reaction.

  The present invention further provides an insulating film made of a polymer having the pore structure.

  The present invention further provides a method for producing an insulating film, comprising: applying an insulating film-forming material on a substrate; and then subjecting the material to a polymerization reaction to form an insulating film made of a polymer having a pore structure. I will provide a.

［式中、Ｘ¹は２〜４価の芳香族又は非芳香族環式基を示す。Ｙ^1a、Ｙ^1bは、同一又は異なって、単結合、２価の芳香族炭化水素基、２価の芳香族複素環式基、２価の芳香族複素環式基の前駆体に相当する２価の基、又はこれらの基が２以上結合した２価の基を示す。但し、Ｙ^1a、Ｙ^1bのうち少なくとも一方は、２価の芳香族複素環式基、又は２価の芳香族複素環式基の前駆体に相当する２価の基を含む基である。Ｗ¹は少なくともアルキレン基又はエーテル結合を少なくとも含む全原子数２〜２０の２価の基からなるフレキシブルユニットを示す。Ｚ¹はカルボキシル基、置換オキシカルボニル基、ホルミル基、ハロホルミル基、置換基を有していてもよいエチニル基を含む基、３，４−ジアミノフェニル基、３−アミノ−４−ヒドロキシフェニル基、４−アミノ−３−ヒドロキシフェニル基、３−アミノ−４−メルカプトフェニル基又は４−アミノ−３−メルカプトフェニル基を示す。Ｒ¹は、水素原子又は炭化水素基を示す。ｎ１は２〜４の整数を示し、ｎ２は０〜２の整数を示す。ｎ１＋ｎ２＝２〜４である。分子内の複数のＹ^1a、Ｙ^1b、Ｗ¹、Ｚ¹、及び複数存在する場合のＲ¹は、それぞれ同一であっても異なっていてもよい］
で表される重合性化合物を提供する。 The present invention also provides the following formula (7):

[Wherein, X ¹ represents a divalent to tetravalent aromatic or non-aromatic cyclic group. Y ^1a and Y ^1b are the same or different and represent a single bond, a divalent aromatic hydrocarbon group, a divalent aromatic heterocyclic group, or a precursor of a divalent aromatic heterocyclic group. And a divalent group in which two or more of these groups are bonded. However, at least one of Y ^1a and Y ^1b is a group containing a divalent aromatic heterocyclic group or a divalent group corresponding to a precursor of a divalent aromatic heterocyclic group. W ¹ represents a flexible unit composed of a divalent group having 2 to 20 atoms in total containing at least an alkylene group or an ether bond. Z ¹ represents a carboxyl group, a substituted oxycarbonyl group, a formyl group, a haloformyl group, a group containing an optionally substituted ethynyl group, a 3,4-diaminophenyl group, a 3-amino-4-hydroxyphenyl group, A 4-amino-3-hydroxyphenyl group, a 3-amino-4-mercaptophenyl group or a 4-amino-3-mercaptophenyl group is shown. R ¹ represents a hydrogen atom or a hydrocarbon group. n1 shows the integer of 2-4, n2 shows the integer of 0-2. n1 + n2 = 2-4. A plurality of Y ^1a , Y ^1b , W ¹ , Z ¹ in the molecule, and R ¹ in the case where a plurality exist may be the same or different.]
The polymerizable compound represented by these is provided.

At least one of Y ^1a and Y ^1b is a divalent aromatic heterocyclic group containing a benzimidazole ring, benzoxazole ring or benzthiazole ring, or a precursor of the divalent aromatic heterocyclic group. The corresponding divalent group is preferred.

［式中、Ｙ¹は、２価の芳香族複素環式基、又は２価の芳香族複素環式基の前駆体に相当する２価の基を示す。Ｗはアルキレン基又はエーテル結合を少なくとも含む全原子数２〜２０の２〜４価の基からなるフレキシブルユニットを示す。Ｚ¹はカルボキシル基、置換オキシカルボニル基、ホルミル基、ハロホルミル基、置換基を有していてもよいエチニル基を含む基、３，４−ジアミノフェニル基、３−アミノ−４−ヒドロキシフェニル基、４−アミノ−３−ヒドロキシフェニル基、３−アミノ−４−メルカプトフェニル基又は４−アミノ−３−メルカプトフェニル基を示す。ｎは２〜４の整数を示す。分子内の複数のＹ¹、Ｚ¹はそれぞれ同一であっても異なっていてもよい］
で表される重合性化合物を提供する。 The present invention further provides the following formula (8):

[Wherein Y ¹ represents a divalent aromatic heterocyclic group or a divalent group corresponding to a precursor of a divalent aromatic heterocyclic group. W represents a flexible unit composed of a divalent to tetravalent group having 2 to 20 atoms and containing at least an alkylene group or an ether bond. Z ¹ represents a carboxyl group, a substituted oxycarbonyl group, a formyl group, a haloformyl group, a group containing an optionally substituted ethynyl group, a 3,4-diaminophenyl group, a 3-amino-4-hydroxyphenyl group, A 4-amino-3-hydroxyphenyl group, a 3-amino-4-mercaptophenyl group or a 4-amino-3-mercaptophenyl group is shown. n shows the integer of 2-4. Plural Y ¹ and Z ¹ in the molecule may be the same or different.
The polymerizable compound represented by these is provided.

Y ¹ represents a divalent aromatic heterocyclic group containing a benzimidazole ring, a benzoxazole ring or a benzthiazole ring, or a divalent group corresponding to a precursor of the divalent aromatic heterocyclic group. Preferably there is.

［式中、Ｘ¹は２〜４価の有機基を示す。Ｙ^1a、Ｙ^1b、Ｙ^2a、Ｙ^2bは、同一又は異なって、単結合、２価の芳香族炭化水素基、２価の芳香族複素環式基、２価の芳香族複素環式基の前駆体に相当する２価の基、又はこれらの基が２以上結合した２価の基を示す。但し、Ｙ^1a、Ｙ^1bのうち少なくとも一方は、２価の芳香族複素環式基、又は２価の芳香族複素環式基の前駆体に相当する２価の基を含む基である。Ｗ¹、Ｗ²は、同一又は異なって、アルキレン基又はエーテル結合を少なくとも含む全原子数２〜２０の２価の基からなるフレキシブルユニットを示す。Ｚ¹、Ｚ²は、それぞれ、カルボキシル基、置換オキシカルボニル基、ホルミル基、ハロホルミル基、置換基を有していてもよいエチニル基を含む基、３，４−ジアミノフェニル基、３−アミノ−４−ヒドロキシフェニル基、４−アミノ−３−ヒドロキシフェニル基、３−アミノ−４−メルカプトフェニル基又は４−アミノ−３−メルカプトフェニル基を示す。Ｒ¹は、水素原子又は炭化水素基を示す。ｋは０又は１を示す。ｐ１、ｐ２は、それぞれ１〜３の整数を示し、ｐ３は０〜２の整数を示す。ｐ１＋ｐ２＋ｐ３＝２〜４である。分子内に複数存在する場合のＹ^1a、Ｙ^1b、Ｙ^2a、Ｙ^2b、Ｗ¹、Ｗ²、Ｚ¹、Ｚ²、Ｒ¹は、それぞれ同一であっても異なっていてもよい］
で表される重合性化合物を提供する。 The present invention further provides the following formula (9):

[Wherein, X ¹ represents a divalent to tetravalent organic group. Y ^1a , Y ^1b , Y ^2a and Y ^2b are the same or different and are each a single bond, a divalent aromatic hydrocarbon group, a divalent aromatic heterocyclic group or a divalent aromatic heterocyclic group. A divalent group corresponding to a precursor or a divalent group in which two or more of these groups are bonded to each other is shown. However, at least one of Y ^1a and Y ^1b is a group containing a divalent aromatic heterocyclic group or a divalent group corresponding to a precursor of a divalent aromatic heterocyclic group. W ¹ and W ² are the same or different and each represents a flexible unit comprising a divalent group having 2 to 20 atoms and containing at least an alkylene group or an ether bond. Z ¹ and Z ² are each a carboxyl group, a substituted oxycarbonyl group, a formyl group, a haloformyl group, a group containing an optionally substituted ethynyl group, 3,4-diaminophenyl group, 3-amino- 4-hydroxyphenyl group, 4-amino-3-hydroxyphenyl group, 3-amino-4-mercaptophenyl group or 4-amino-3-mercaptophenyl group is shown. R ¹ represents a hydrogen atom or a hydrocarbon group. k represents 0 or 1. p1 and p2 each represent an integer of 1 to 3, and p3 represents an integer of 0 to 2. p1 + p2 + p3 = 2-4. Y ^1a , Y ^1b , Y ^2a , Y ^2b , W ¹ , W ² , Z ¹ , Z ² , R ¹ in the case where there are a plurality in the molecule may be the same or different.
The polymerizable compound represented by these is provided.

At least one of Y ^1a and Y ^1b is a divalent aromatic heterocyclic group containing a benzimidazole ring, benzoxazole ring or benzthiazole ring, or a precursor of the divalent aromatic heterocyclic group. The corresponding divalent group is preferred.

At least one of Y ^2a and Y ^2b is a divalent aromatic heterocyclic group containing a benzimidazole ring, benzoxazole ring or benzthiazole ring, or a precursor of the divalent aromatic heterocyclic group. It is preferably a divalent group corresponding to the body.

  The insulating film forming material of the present invention is a flexible unit in which at least one of two compounds capable of forming a polymer having a pore structure or one compound capable of forming a polymer having a pore structure is a specific structure. Since the molecular chain is easy to move and the reaction between functional groups or groups of functional groups occurs surely during polymerization, the polymer and insulation having a pore structure with low dielectric constant and little variation in dielectric constant A membrane can be obtained. The insulating film thus obtained also has high heat resistance and mechanical strength. The polymerizable compound of the present invention can be used as a constituent component (monomer component) of the insulating film forming material having such excellent characteristics.

The insulating film forming material of the present invention has two or more functional groups or functional group groups in the molecule of each compound, and the functional group or functional group group of one compound and the functional group or functional group of the other compound. Two compounds A and B that can be polymerized by bonding with a group of groups to form a polymer having a pore structure, and / or have two or more functional groups or groups of functional groups in the molecule An insulating film forming material comprising a compound C capable of forming a polymer having a pore structure by polymerizing by bonding of one functional group or functional group and another functional group or functional group, The compound A, the compound B, and the compound C satisfy the following condition (i) or (ii).
(I) At least one of Compound A and Compound B has a bridged alicyclic skeleton or an aromatic ring skeleton as a central skeleton, and at least one of Compound A and Compound B is a central skeleton and the functional group or functional group group Having a heat-resistant skeleton composed of a divalent organic group containing an aromatic ring, and at least one of compound A and compound B having 2 to 20 atoms in total containing at least an alkylene group or an ether bond in the molecule A pair of functional groups or functional groups having a flexible unit composed of an organic group and capable of forming a heterocyclic ring by reacting the functional group or functional group group of compound A and the functional group or functional group group of compound B with each other. (Ii) Compound C has a bridged alicyclic skeleton or an aromatic ring skeleton as a central skeleton, and is a group that includes an ethynyl group that may have a substituent. Said one officer A heat-resistant skeleton composed of a divalent organic group containing an aromatic ring between the group or functional group and / or between the central skeleton and another functional group or functional group, A flexible unit comprising an organic group having 2 to 20 atoms in total containing at least an alkylene group or an ether bond between the functional group or the functional group of and / or between the central skeleton and another functional group or the functional group. And one functional group or functional group group of compound C and another functional group or functional group group are a pair of functional groups or functional groups capable of reacting with each other to form a heterocyclic ring, Or a group containing an ethynyl group which may have a substituent.

  In this specification, the case of having two functional groups or groups of functional groups involved in polymerization is referred to as “bifunctional”, the case of having three, “trifunctional”, and the case of having four are referred to as “tetrafunctional”. There is.

  In general, when a polymer having a pore structure (high molecular weight polymer) is formed from two types of compounds X and Y, examples of the combination of the compounds X and Y include a plurality of (for example, 2 to 4) bonded to the central skeleton. A plurality of (for example, 2 to 4, preferably 2) functional groups or functional groups, each of which is a compound X having a two-dimensional structure or a three-dimensional structure. The combination with the compound Y which makes | forms a dimensional structure (linear form) or a two-dimensional structure (linear form with an angle) is mentioned. In this case, the compound X forms a nodal point or cross-linking point (vertex) of the polymer, and the compound Y forms a connecting portion (side) connecting the nodal point or cross-linking point. Holes are formed at sites surrounded by some nodes or bridge points and some connections. The polymer may be a polymer having a branched structure (particularly a multi-branched structure) (polymer crosslinked product), or may be a polymer composed of chain-like polymer molecules having no branch. Even in the case of a polymer composed of a chain-like polymer molecule having no branch, penetration of other molecular chains into a region where one polymer molecule exists is suppressed due to the excluded volume effect between segments in the polymer molecular chain, As a result, a relatively sparse filling structure is formed. Such a structure is also included in the pore structure.

  In the present invention, at least one of the compound A and the compound B, and the compound C have a bridged alicyclic skeleton or an aromatic ring skeleton as a central skeleton.

  As representative examples of the bridged alicyclic ring or aromatic ring related to the bridged alicyclic skeleton or aromatic ring skeleton as the central skeleton, the rings represented by the formulas (4a) to (4o), or two or more of these ( For example, 2-3 rings) may be mentioned. In formula (4j), r is an integer of 0 to 5, preferably an integer of 0 to 2.

  Preferred examples of the bridged alicyclic skeleton or aromatic ring skeleton as the central skeleton include adamantane skeleton, biadamantane skeleton, tetraphenyladamantane skeleton, norbornane skeleton, tetramethylnorbornane skeleton, norbornene skeleton, tetramethylnorbornene skeleton and the like. Examples include bridged alicyclic skeletons; aromatic ring skeletons including aromatic rings such as tetraphenylmethane skeleton, benzene skeleton, naphthalene skeleton, and biphenyl skeleton. The molecular weight of the central skeleton is, for example, about 40 to 1460, preferably about 60 to 500.

  The functional group is not particularly limited as long as it has reactivity, but representative examples include a carboxyl group, an amino group, a hydroxyl group, a mercapto group, a formyl group, a silanol group, a halogen atom, a carbanion, and a substituent. And an ethynyl group which may have a group or a group containing these. In addition, these groups may be derivatized into reactive groups and may be protected with a protecting group. Examples of the reactive group include a haloformyl group, an acid anhydride group (which can also be classified as a carboxyl group protected by a protecting group) and the like in the carboxyl group. As the protecting group, a protecting group conventionally used in the field of organic synthesis can be used. For example, examples of the carboxyl group protected by a protecting group include alkoxycarbonyl groups such as methoxycarbonyl and ethoxycarbonyl groups, and substituted oxycarbonyl groups such as benzyloxycarbonyl groups. Examples of the amino group protected with a protecting group include an acylamino group such as an acetylamino group, an amino group protected with an alkylidene group, a cycloalkylidene group, a benzylidene group, etc. (imine derivative), an alkoxycarbonyl group, and an aralkylcarboxyl group. Examples include a protected amino group (carbamic acid ester derivative). One of the two hydrogen atoms of the amino group may be a mono-substituted amino group substituted with an alkyl group such as a methyl group or a phenyl group. Examples of the hydroxyl group protected with a protecting group include acyloxy groups such as acetyloxy group, hydroxyl groups protected with aldehyde (acetal, hemiacetal derivatives), and the like.

  Examples of combinations of functional groups or functional groups that react with each other to form chemical bonds include, for example, a combination of a carboxyl group and an amino group (formation of an amide bond), a combination of a carboxyl group and a hydroxyl group (formation of an ester bond) ), Carboxyl group and mercapto group (thioester bond formation), hydroxyl group and hydroxyl group combination (ether bond formation), hydroxyl group and mercapto group combination (thioether bond formation), carbon-carbon A combination of two functional groups capable of forming a bond, a combination of two functional groups capable of forming a carbon-nitrogen bond; two bonded to one carboxyl group and the 1,2- or 1,3-position carbon atom In combination with an amino group (5- or 6-membered ring having two nitrogen atoms such as an imidazole ring) Formation) Combination of one formyl group and two amino groups bonded to the 1,2- or 1,3-position carbon atoms (under nitrogen conditions such as oxygen atmosphere, two nitrogen atoms such as imidazole ring) A 5-membered or 6-membered ring having a single group, a combination of one carboxyl group and an amino group and a hydroxyl group bonded to the 1,2- or 1,3-position carbon atom (one nitrogen atom such as an oxazole ring) And formation of a 5- or 6-membered ring having one oxygen atom), one carboxyl group and one amino group and one mercapto group bonded to the 1,2- or 1,3-position carbon atom (Formation of a 5- or 6-membered ring having one nitrogen atom and one sulfur atom such as a thiazole ring), two carboxyl groups bonded to the 1,2- or 1,3-position carbon atom and 1 Combination with 5 amino groups (5 or Formation of 6-membered imide ring), but like a combination of good ethynyl groups to each other may have a substituent, but is not limited thereto.

  In the present invention, the functional group or functional group of compound A and the functional group or functional group of compound B are a pair of functional groups or functional groups that can react with each other to form a heterocyclic ring, or are substituted together. It is a group containing an ethynyl group which may have a group. Further, one functional group or functional group group of compound C and another functional group or functional group group are a pair of functional groups or functional group groups that can react with each other to form a heterocyclic ring, or both are substituents. Is a group containing an ethynyl group which may have

Preferable examples of the heterocyclic ring include a benzimidazole ring, a benzoxazole ring, and a benzthiazole ring. Among these, a benzimidazole ring and a benzoxazole ring are preferable. Further, as a preferred combination of a pair of functional groups or functional groups capable of forming the heterocyclic ring, one is a carboxyl group, a substituted oxycarbonyl group, a formyl group, or a haloformyl group, and the other is a 3,4-diaminophenyl group, The combination which is 3-amino-4-hydroxyphenyl group, 4-amino-3-hydroxyphenyl group, 3-amino-4-mercaptophenyl group or 4-amino-3-mercaptophenyl group is mentioned. Examples of the substituted oxycarbonyl group include C _1-6 alkoxy-carbonyl groups such as methoxycarbonyl and ethoxycarbonyl groups.

  Examples of the group containing an ethynyl group that may have a substituent include an ethynyl group and an ethynylphenyl group. As a combination of ethynyl groups which may have a substituent, a combination of ethynyl group and ethynylphenyl group is particularly preferable.

  In the present invention, at least one of the compound A and the compound B has a heat-resistant skeleton composed of a divalent organic group containing an aromatic ring between the central skeleton and the functional group or functional group group. Compound C is composed of a divalent organic group containing an aromatic ring between the central skeleton and the one functional group or functional group group and / or between the central skeleton and another functional group or functional group group. Has a heat-resistant skeleton. Thus, since the monomer component constituting the insulating film forming material has a heat resistant skeleton, an insulating film having high heat resistance can be obtained.

  As typical examples of a heat-resistant skeleton composed of a divalent organic group containing an aromatic ring contained in at least one of Compound A and Compound B, and a heat-resistant skeleton composed of a divalent organic group containing an aromatic ring contained in Compound C, Examples include groups represented by the above formulas (5a) to (5p) or a group in which a plurality of these groups (for example, 2 to 3) are bonded. In formula, s is an integer of 0-5, Preferably it is an integer of 0-2. Of these, a group in which a hydroxyl group is bonded to a benzene ring is also preferably a group in which the hydroxyl group is replaced with a mercapto group.

  In the present invention, at least one of the compound A and the compound B has a flexible unit composed of an organic group having 2 to 20 atoms in total containing at least an alkylene group or an ether bond in the molecule. In addition, the compound C has a total number of atoms including at least an alkylene group or an ether bond between the central skeleton and the one functional group or functional group group and / or between the central skeleton and another functional group or functional group group. It has a flexible unit composed of 2 to 20 organic groups. Thus, since the monomer component constituting the insulating film forming material has a flexible unit that easily moves during the reaction (at the time of polymerization), the functional group or the functional group reliably reacts, and the unreacted functional group Since it is difficult to remain, the value of the dielectric constant can be further reduced, and variations in the dielectric constant can be reduced.

  As a typical example of a flexible unit composed of an organic group having 2 to 20 atoms in total including at least one of the compound A and the compound B or the alkylene group or ether bond of the compound C, the above formulas (6a) to (6) And a flexible unit comprising the group represented by 6j). In formula, t is an integer of 1-19, Preferably it is an integer of 1-10. u is an integer of 1 to 10, preferably an integer of 1 to 5. v is an integer of 1 to 3, and preferably an integer of 1 to 2. w is an integer of 1 to 16, preferably an integer of 1 to 8. x is an integer of 1-14, preferably an integer of 1-7. y and z are each an integer of 0 to 6, preferably an integer of 0 to 4. However, y and z are not 0 at the same time.

  In the insulating film forming material of the present invention, it is preferable that the compound A, the compound B, and the compound C satisfy the following condition (iii) or (iv). That is, (iii) Compound A is a compound represented by Formula (1a) or a compound represented by Formula (1b), and Compound B is a compound represented by Formula (2), or (Iv) It is preferable that the compound C is a compound represented by the formula (3).

In the formula (1a), X ¹ represents a divalent to tetravalent bridged alicyclic group or aromatic cyclic group. Y ^1a and Y ^1b are the same or different and represent a single bond, a divalent aromatic hydrocarbon group, a divalent aromatic heterocyclic group, or a precursor of a divalent aromatic heterocyclic group. And a divalent group in which two or more of these groups are bonded. W ¹ represents a flexible unit composed of a divalent group having 2 to 20 atoms and containing at least an alkylene group or an ether bond. Z ¹ is a group containing a functional group or a functional group capable of reacting with Z ² in the following formula (2) to form a heterocyclic ring, or an ethynyl group optionally having a substituent (provided that the formula (2) In which Z ² is a group containing an ethynyl group which may have a substituent. R ¹ represents a hydrogen atom or a hydrocarbon group. n1 shows the integer of 2-4, n2 shows the integer of 0-2. n1 + n2 = 2-4. A plurality of Y ^1a , Y ^1b , W ¹ , Z ¹ in the molecule and R ¹ in the case where a plurality exist may be the same or different.

The bridged alicyclic or aromatic ring related to the divalent to tetravalent bridged alicyclic group or aromatic cyclic group in X ¹ includes at least one of the compounds A and B, and a compound as a central skeleton of the compound C. Examples thereof include the rings represented by the formulas (4a) to (4p) exemplified as the bridged alicyclic ring or aromatic ring related to the bridging alicyclic group or aromatic cyclic group. Among these, a bridged alicyclic ring, particularly an adamantane ring [ring represented by the formula (4a)] or a biadamantane ring is preferable. The valence of X ¹ is preferably trivalent or tetravalent, particularly tetravalent.

Examples of the divalent aromatic hydrocarbon group for Y ^1a and Y ^1b include a phenylene group and a naphthylene group. Examples of the aromatic heterocyclic ring related to the divalent aromatic heterocyclic group include a benzimidazole ring, a benzoxazole ring, and a benzthiazole ring. Examples of the divalent group corresponding to the precursor of the divalent aromatic heterocyclic group include groups that form an aromatic heterocyclic group by ring closure. For example, the ring corresponding to the precursor of the benzimidazole ring includes a ring in which an amino group and an acylamino group are bonded to the ortho position of the benzene ring. Further, examples of the ring corresponding to the precursor of the benzoxazole ring include a ring in which a hydroxyl group and an acylamino group are bonded to an ortho position of the benzene ring. Further, examples of the ring corresponding to the precursor of the benzthiazole ring include a ring in which a mercapto group and an acylamino group are bonded to the ortho position of the benzene ring.

Y ^1a and Y ^1b are described as typical examples of a heat-resistant skeleton composed of a divalent organic group containing an aromatic ring in addition to a single bond, at least one of the compounds A and B, and the compound C. Examples include groups represented by formulas (5a) to (5p). In formula, s is an integer of 0-5, Preferably it is an integer of 0-2. Of these, a group in which a hydroxyl group is bonded to a benzene ring is also preferably a group in which the hydroxyl group is replaced with a mercapto group.

The flexible unit composed of a divalent group having 2 to 20 atoms in total including at least an alkylene group or an ether bond in W ¹ includes at least one of the compounds A and B and an alkylene group or an ether bond that the compound C has. The flexible unit which consists of group represented by the said Formula (6a)-(6j) described as a typical example of the flexible unit which consists of a 2-20 total atom organic group to contain is mentioned. In formula, t is an integer of 1-19, Preferably it is an integer of 1-10. u is an integer of 1 to 10, preferably an integer of 1 to 5. v is an integer of 1 to 3, and preferably an integer of 1 to 2. w is an integer of 1 to 16, preferably an integer of 1 to 8. x is an integer of 1-14, preferably an integer of 1-7. y and z are each an integer of 0 to 6, preferably an integer of 0 to 4. However, y and z are not 0 at the same time.

The functional group or functional group that can form a heterocyclic ring by reacting with Z ² in Z ^{1 includes a} functional group or a functional group that can react with Z ² to form a benzimidazole ring, a benzoxazole ring, a benzthiazole ring, or the like. Group, for example, when Z ² is a carboxyl group, a substituted oxycarbonyl group, a formyl group or a haloformyl group, 3,4-diaminophenyl group, 3-amino-4-hydroxyphenyl group, 4-amino-3 -Hydroxyphenyl group, 3-amino-4-mercaptophenyl group, 4-amino-3-mercaptophenyl group and the like are exemplified, and Z ² is 3,4-diaminophenyl group, 3-amino-4-hydroxyphenyl group, 4-amino-3-hydroxyphenyl group, 3-amino-4-mercaptophenyl group or 4-amino-3-mercaptophenyl group In some cases, examples include a carboxyl group, a substituted oxycarbonyl group, a formyl group, or a haloformyl group. Examples of the substituted oxycarbonyl group include C _1-6 alkoxy-carbonyl groups such as methoxycarbonyl and ethoxycarbonyl groups.

Examples of the group containing an ethynyl group which may have a substituent in Z ¹ include an ethynyl group and an ethynylphenyl group. In the case Z ² is ethynyl group, Z ¹ is preferably ethynylphenyl group, if Z ² is an ethynylphenyl group, Z ¹ is an ethynyl group is preferred.

Examples of the hydrocarbon group for R ¹ include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group in which these are bonded. Examples of the aliphatic hydrocarbon group include 1 to 20 carbon atoms (preferably 1 to 1) such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, decyl, and dodecyl groups. 10 or more preferably 1 to 6) linear or branched alkyl group; 2 to 20 carbon atoms (preferably 2 to 10) such as vinyl, allyl, 1-butenyl, 3-methyl-4-pentenyl group, etc. And more preferably about 2 to 5) linear or branched alkenyl group; ethynyl, propynyl, 1-butynyl, 2-butynyl group and the like having 2 to 20 carbon atoms (preferably 2 to 10, more preferably 2). -5) about a linear or branched alkynyl group.

  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 (preferably 6 to 14) carbon atoms such as phenyl and naphthyl 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 and the like). The hydrocarbon group in which an aliphatic hydrocarbon group and an aromatic hydrocarbon group are bonded to each other includes an aralkyl group (for example, a C _7-18 aralkyl group) and an alkyl-substituted aryl group (for example, about 1 to about 4). A phenyl group substituted with a C _1-4 alkyl group or a naphthyl group).

  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 properties of the reaction and the crosslinked polymer.

Among the compounds represented by the formula (1a), the compound represented by the formula (7) is important. In formula (7), X ¹ represents a divalent to tetravalent aromatic or non-aromatic cyclic group. Y ^1a and Y ^1b are the same or different and represent a single bond, a divalent aromatic hydrocarbon group, a divalent aromatic heterocyclic group, or a precursor of a divalent aromatic heterocyclic group. And a divalent group in which two or more of these groups are bonded. However, at least one of Y ^1a and Y ^1b is a group containing a divalent aromatic heterocyclic group or a divalent group corresponding to a precursor of a divalent aromatic heterocyclic group. W ¹ represents a flexible unit composed of a divalent group having 2 to 20 atoms in total containing at least an alkylene group or an ether bond. Z ¹ represents a carboxyl group, a substituted oxycarbonyl group, a formyl group, a haloformyl group, a group containing an optionally substituted ethynyl group, a 3,4-diaminophenyl group, a 3-amino-4-hydroxyphenyl group, A 4-amino-3-hydroxyphenyl group, a 3-amino-4-mercaptophenyl group or a 4-amino-3-mercaptophenyl group is shown. R ¹ represents a hydrogen atom or a hydrocarbon group. n1 shows the integer of 2-4, n2 shows the integer of 0-2. n1 + n2 = 2-4. A plurality of Y ^1a , Y ^1b , W ¹ , Z ¹ in the molecule and R ¹ in the case where a plurality exist may be the same or different. At least one of Y ^1a and Y ^1b is a divalent aromatic heterocyclic group containing a benzimidazole ring, a benzoxazole ring or a benzthiazole ring, or a precursor of the divalent aromatic heterocyclic group. The corresponding divalent group is preferred.

  The compound represented by formula (7) can be synthesized using a known compound as a starting material and using a known reaction such as a condensation reaction, a substitution reaction, an addition reaction, an oxidation reaction, or a cyclization reaction.

  Representative examples of the compound represented by the formula (1a) include compounds represented by the following formula.

In formula (1b), Y ¹ is a divalent divalent aromatic precursor, a divalent aromatic hydrocarbon group, a divalent aromatic heterocyclic group, a divalent aromatic heterocyclic group precursor corresponding to a divalent precursor. Or a divalent group in which two or more of these groups are bonded. W represents a flexible unit composed of a divalent to tetravalent group having 2 to 20 atoms and containing at least an alkylene group or an ether bond. Z ¹ is a group containing a functional group or a functional group capable of reacting with Z ² in the following formula (2) to form a heterocyclic ring, or an ethynyl group optionally having a substituent (provided that the formula (2) In which Z ² is a group containing an ethynyl group which may have a substituent. n shows the integer of 2-4. A plurality of Y ¹ and Z ¹ in the molecule may be the same or different.

Divalent aromatic hydrocarbon group for Y ^1, divalent aromatic heterocyclic group, a divalent divalent group corresponding to a precursor of the aromatic heterocyclic group, said Y ^1a, the Y ^1b This is the same as the divalent group corresponding to the divalent aromatic hydrocarbon group, the divalent aromatic heterocyclic group, and the precursor of the divalent aromatic heterocyclic group.

The flexible unit consisting of a divalent to tetravalent group having 2 to 20 total atoms including at least an alkylene group or an ether bond in W is a divalent group having 2 to 20 total atoms including at least an alkylene group or an ether bond in W ¹ . It is the same as that of the flexible unit which consists of. Z ¹ is the same as described above.

Among the compounds represented by the formula (1b), the compound represented by the formula (8) is important. In Formula (8), Y ¹ represents a divalent group corresponding to a divalent aromatic heterocyclic group or a precursor of a divalent aromatic heterocyclic group. W represents a flexible unit composed of a divalent to tetravalent group having 2 to 20 atoms and containing at least an alkylene group or an ether bond. Z ¹ represents a carboxyl group, a substituted oxycarbonyl group, a formyl group, a haloformyl group, a group containing an optionally substituted ethynyl group, a 3,4-diaminophenyl group, a 3-amino-4-hydroxyphenyl group, A 4-amino-3-hydroxyphenyl group, a 3-amino-4-mercaptophenyl group or a 4-amino-3-mercaptophenyl group is shown. n shows the integer of 2-4. A plurality of Y ¹ and Z ¹ in the molecule may be the same or different. Y ¹ represents a divalent aromatic heterocyclic group containing a benzimidazole ring, a benzoxazole ring or a benzthiazole ring, or a divalent group corresponding to a precursor of the divalent aromatic heterocyclic group. Preferably there is.

  The compound represented by formula (8) can be synthesized using a known compound as a starting material and using a known reaction such as a condensation reaction, a substitution reaction, an addition reaction, an oxidation reaction, or a cyclization reaction.

  Representative examples of the compound represented by the formula (1b) include compounds represented by the following formula.

In formula (2), X ² represents a divalent to tetravalent bridged alicyclic group or aromatic cyclic group. Y ^2a and Y ^2b are the same or different and represent a single bond, a divalent aromatic hydrocarbon group, a divalent aromatic heterocyclic group, or a precursor of a divalent aromatic heterocyclic group. And a divalent group in which two or more of these groups are bonded. W ² represents a flexible unit composed of a divalent group having 2 to 20 atoms in total containing at least an alkylene group or an ether bond. Z ² represents a functional group or a group of functional groups that can form a heterocyclic ring by reacting with Z ¹ in the formula (1a) or (1b), or a group containing an ethynyl group which may have a substituent (provided that Z ¹ in formula (1a) or (1b) is limited to a group containing an ethynyl group which may have a substituent. R ² represents a hydrogen atom or a hydrocarbon group. m1 represents an integer of 2 to 4, and m2 represents an integer of 0 to 2. m1 + m2 = 2-4. i represents 0 or 1, and k represents 0 or 1. A plurality of Y ^2a , Y ^2b , W ² , Z ² in the molecule, and R ² when there are a plurality thereof may be the same or different.

The divalent to tetravalent bridged alicyclic group and aromatic cyclic group in X ² are the same as the divalent to tetravalent bridged alicyclic group and aromatic cyclic group in X ¹ . The divalent group corresponding to the precursor of the divalent aromatic hydrocarbon group, divalent aromatic heterocyclic group, divalent aromatic heterocyclic group in Y ^2a and Y ^2b is Y ^1a , This is the same as the divalent group corresponding to the divalent aromatic hydrocarbon group, divalent aromatic heterocyclic group, divalent aromatic heterocyclic group precursor of Y ^1b . The flexible unit comprising a divalent group having 2 to 20 atoms in total containing at least an alkylene group or an ether bond in W ² is a divalent group having 2 to 20 atoms in total containing at least an alkylene group or an ether bond in W ¹ . It is the same as the flexible unit comprising the base.

The functional group or functional group that can form a heterocyclic ring by reacting with Z ¹ in Z ² is a functional group or functional group that can react with Z ¹ to form a benzimidazole ring, a benzoxazole ring, a benzthiazole ring or the like. Group, for example, when Z ¹ is a carboxyl group, a substituted oxycarbonyl group, a formyl group or a haloformyl group, 3,4-diaminophenyl group, 3-amino-4-hydroxyphenyl group, 4-amino-3 -Hydroxyphenyl group, 3-amino-4-mercaptophenyl group, 4-amino-3-mercaptophenyl group and the like are exemplified, and Z ¹ is 3,4-diaminophenyl group, 3-amino-4-hydroxyphenyl group, 4-amino-3-hydroxyphenyl group, 3-amino-4-mercaptophenyl group or 4-amino-3-mercaptophenyl group In some cases, examples include a carboxyl group, a substituted oxycarbonyl group, a formyl group, or a haloformyl group. Examples of the substituted oxycarbonyl group include C _1-6 alkoxy-carbonyl groups such as methoxycarbonyl and ethoxycarbonyl groups.

Examples of the group containing an ethynyl group that may have a substituent in Z ² include an ethynyl group and an ethynylphenyl group. In the case Z ¹ is ethynyl group, Z ² is preferably ethynylphenyl group, if Z ¹ is a ethynylphenyl group, Z ² is an ethynyl group is preferable.

The hydrocarbon group for R ² is the same as the hydrocarbon group for R ¹ .

Of the compounds represented by the formula (2), the compound represented by the formula (9) is important. In formula (9), X ¹ represents a divalent to tetravalent organic group. Y ^1a , Y ^1b , Y ^2a and Y ^2b are the same or different and are each a single bond, a divalent aromatic hydrocarbon group, a divalent aromatic heterocyclic group or a divalent aromatic heterocyclic group. A divalent group corresponding to a precursor or a divalent group in which two or more of these groups are bonded to each other is shown. However, at least one of Y ^1a and Y ^1b is a group containing a divalent aromatic heterocyclic group or a divalent group corresponding to a precursor of a divalent aromatic heterocyclic group. W ¹ and W ² are the same or different and each represents a flexible unit comprising a divalent group having 2 to 20 atoms and containing at least an alkylene group or an ether bond. Z ¹ and Z ² are each a carboxyl group, a substituted oxycarbonyl group, a formyl group, a haloformyl group, a group containing an optionally substituted ethynyl group, 3,4-diaminophenyl group, 3-amino- 4-hydroxyphenyl group, 4-amino-3-hydroxyphenyl group, 3-amino-4-mercaptophenyl group or 4-amino-3-mercaptophenyl group is shown. R ¹ represents a hydrogen atom or a hydrocarbon group. k represents 0 or 1. p1 and p2 each represent an integer of 1 to 3, and p3 represents an integer of 0 to 2. p1 + p2 + p3 = 2-4. Y ^1a , Y ^1b , Y ^2a , Y ^2b , W ¹ , W ² , Z ¹ , Z ² , and R ¹ in the case where a plurality exist in the molecule may be the same or different. At least one of Y ^1a and Y ^1b is a divalent aromatic heterocyclic group containing a benzimidazole ring, a benzoxazole ring or a benzthiazole ring, or a precursor of the divalent aromatic heterocyclic group. The corresponding divalent group is preferred. In addition, at least one of Y ^2a and Y ^2b is a divalent aromatic heterocyclic group containing a benzimidazole ring, a benzoxazole ring or a benzthiazole ring, or a precursor of the divalent aromatic heterocyclic group. A divalent group corresponding to is preferred.

  The compound represented by the formula (9) can be synthesized using a known compound as a starting material and using a known reaction such as a condensation reaction, a substitution reaction, an addition reaction, an oxidation reaction, or a cyclization reaction.

  A typical example of the compound represented by the formula (2) is a compound represented by the following formula.

In Formula (3), X ¹ represents a divalent to tetravalent bridged alicyclic group or aromatic cyclic group. Y ^1a , Y ^1b , Y ^2a and Y ^2b are the same or different and are each a single bond, a divalent aromatic hydrocarbon group, a divalent aromatic heterocyclic group or a divalent aromatic heterocyclic group. A divalent group corresponding to a precursor or a divalent group in which two or more of these groups are bonded to each other is shown. W ¹ and W ² are the same or different and each represents a flexible unit comprising a divalent group having 2 to 20 atoms and containing at least an alkylene group or an ether bond. Z ¹ and Z ² are a functional group or a group of functional groups that can form a heterocycle by reacting with each other, or both Z ¹ and Z ² may have a substituent. A substituent containing a group is shown. R ¹ represents a hydrogen atom or a hydrocarbon group. k represents 0 or 1. p1 and p2 each represent an integer of 1 to 3, and p3 represents an integer of 0 to 2. p1 + p2 + p3 = 2-4. Y ^1a , Y ^1b , Y ^2a , Y ^2b , W ¹ , W ² , Z ¹ , Z ² , and R ¹ in the case where a plurality exist in the molecule may be the same or different.

2-4 valent bridged alicyclic group in X ^1, aromatic cyclic ^{group, Y 1a, Y 1b, Y} 2a, 2 divalent aromatic hydrocarbon group for Y ^2b, 2-valent aromatic heterocyclic A flexible group consisting of a divalent group corresponding to a precursor of a group, a divalent aromatic heterocyclic group, a divalent group having 2 to 20 atoms and at least an alkylene group or an ether bond in W ¹ and W ² The units, Z ¹ , Z ² and R ¹ are the same as described above.

  The compound represented by the formula (3) can be synthesized using a known compound as a starting material and using a known reaction such as a condensation reaction, a substitution reaction, an addition reaction, an oxidation reaction, or a cyclization reaction.

  A typical example of the compound represented by the formula (3) is a compound represented by the following formula.

  In the insulating film forming material of the present invention, when compound A and compound B are included, the ratio (molar ratio) is, for example, the former / the latter = 1/99 to 99/1, preferably 10/90 to 90/10. More preferably, it is about 20 / 80-80 / 20, and can also be used in an equivalent amount. Compound A, Compound B, and Compound C can be used alone or in combination of two or more.

  The insulating film forming material of the present invention can be used as a solution in which the compound A, the compound B, and / or the compound C are dissolved in an organic solvent.

  Examples of the organic solvent include amides such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methyl-2-pyrrolidone; dimethylimidazolidine, dimethylimidazolidinone (dimethylimidazolidine-dione), and the like. Cyclic aminoacetals; 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; Formic acid Esters such as ester, acetate ester, propionate ester, benzoate ester, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate (PGMEA); Ethers such as 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, dichloroethane, Halogenated hydrocarbons such as chloroform, carbon tetrachloride, chlorobenzene; nitro compounds such as nitromethane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and mesitylene; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; hexane, Aliphatic hydrocarbons such as heptane and octane; and mixed solvents thereof.

  The insulating 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 Compound A, Compound B, and Compound C. 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 usage-amount of a catalyst is 0-10 mol% with respect to the total amount of the compound A, the compound B, and the compound C, 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 insulating 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 insulating film forming material, for example, Preferably it is about 0-10 weight%. Furthermore, monocarboxylic acids for adjusting the molecular weight after polymerization and / or dicarboxylic acids for adjusting the degree of crosslinking after polymerization may be added to the insulating film forming material of the present invention. Representative examples of monocarboxylic acids include monocarboxylic acids such as adamantane carboxylic acid and benzoic acid; monocarboxylic acid derivatives such as adamantane carboxylic acid methyl ester and benzoic acid methyl ester, and the like. Examples include dicarboxylic acids such as terephthalic acid; dicarboxylic acid derivatives such as dimethyl terephthalate. The usage-amount of monocarboxylic acid is 0-10 mol% with respect to the total amount of the monomer component (Compound A, Compound B, Compound C) which comprises an insulating film formation material, Preferably it is about 0-5 mol%. The amount of dicarboxylic acids used is, for example, about 0 to 100 mol%, preferably about 0 to 50 mol%, based on the total amount of monomer components (compound A, compound B, and compound C) constituting the insulating film forming material. .

  You may add the adhesion promoter for improving the board | substrate adhesiveness of the insulating film formed on a board | substrate to the insulating-film formation 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, for example, about 0 to 10% by weight, preferably about 0 to 5% by weight, based on the total amount of monomer components (compound A, compound B, and compound C) constituting the insulating film forming material. .

  The dissolution of the monomer components (compound A, compound B, compound C) and other components in the organic solvent may be performed, for example, in an air atmosphere as long as the monomer components are not oxidized, but preferably nitrogen, argon, etc. In an inert gas atmosphere. The temperature at which the monomer component and the like are dissolved is not particularly limited, and may be heated according to the solubility and stability of the monomer component and the boiling point of the solvent, for example, 0 to 200 ° C., preferably 10 to 150 ° C. Degree.

  The concentration of the monomer component (compound A, compound B, compound C) in the insulating film forming material can be appropriately selected in consideration of the solubility, coatability, workability, etc. of the monomer component, for example, 5 to 70% by weight, preferably Is about 10 to 60% by weight.

  More specifically, for example, the polymer and insulating film having a pore structure of the present invention may be heated (for example, by applying the above-described insulating film forming material as a coating liquid onto a substrate and then subjecting it to a reaction. It can be obtained by polymerization or cyclization reaction such as by baking. 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 the monomer component can be converted into a high molecular weight polymer, but is generally 25 to 500 ° C (eg 100 to 500 ° C), preferably 25 to 450 ° C (eg 150 to 450 ° C). Degree. 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.

  By heating, the monomer component becomes high molecular weight by polycondensation or the like, and a corresponding polymer (high molecular weight polymer) is generated. In addition, when the monomer component is a compound having a precursor structure of the final structure, a polymer having a desired structure (high molecular weight polymer) is usually obtained as the monomer component has a high molecular weight and a cyclization reaction proceeds. Generate. When the monomer component has a protecting group, usually a high molecular weight or cyclization reaction proceeds with elimination of the protecting group. By the cyclization reaction, an imidazole ring, an oxazole ring, a thiazole ring, or the like is formed from each precursor structure.

  For example, when a tetrafunctional compound is used as the monomer component, a structure (three hexagons sharing two sides with each other) crossed in four directions with a central skeleton (for example, adamantane skeleton) as a vertex (crosslinking point) A network-like polymer film having a unit) and a large number of pores can be formed. When a trifunctional compound is used as the monomer component, a structure in which three hexagons share two vertices or two sides with each other in three directions with a central skeleton (for example, an adamantane skeleton) as a vertex (crosslinking point). A highly crosslinked polymer film having a large number of pores. When a bifunctional compound is used as the monomer component, the exclusion volume effect between segments in the polymer molecular chain restricts the penetration of other molecular chains into the region where one polymer molecule exists, so that from the monomer mixture Compared with the case of directly obtaining a high molecular weight polymer, it is possible to form a polymer film having a sparse packing structure and a high porosity.

  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, an adamantane skeleton), and has a three-dimensionally bulky structure (a structure having a large volume). It has a large molecule. In the polymerization reaction using these as monomer components, the two tetrahedrons prevent the penetration of each other's tetrahedral structure into the space due to extremely large steric hindrance, and the penetration of the growing oligomers, polymers, etc. is also restricted. The 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.

  The insulating film made of the polymer thus formed has a large number of molecular-level vacancies uniformly dispersed therein, and thus has a high porosity and therefore a low dielectric constant. 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. Moreover, since at least one monomer component has a flexible unit, the functional group easily moves, and the reaction between the functional groups is reliably performed. Therefore, the number of unreacted sites is reduced, water absorption due to amino groups, carboxyl groups, and the like can be reduced, the variation in relative permittivity (K value) is eliminated, and the insulation is improved. In addition, when an alternating electric field is applied to the film in dielectric constant measurement, the movable part in the film moves in response to the electric field in response to the vibration of the electric field, and dielectric relaxation, which is a phenomenon of absorbing electric field energy, occurs. Yes. In a conventional film consisting only of a rigid skeleton, many unreacted polar groups remain, so the degree of dielectric relaxation is large, and the variation in measured values of relative permittivity within the same film is remarkable. In a film having a flexible part introduced, the proportion of unreacted highly polar parts is reduced, so that the degree of dielectric relaxation is further suppressed, and a homogeneous film with less variation in measured values of relative permittivity can be obtained. .

  The thickness of the insulating 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 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 insulating 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 components 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 density of the polymer film was determined by analysis of X-ray reflectivity measurement, and 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. “S”, “m”, and “w” in infrared absorption spectrum data indicate “strong” absorption, “medium” absorption, and “weak” absorption, respectively. The weight average molecular weight is a value in terms of polystyrene. The density is a value of 25 ° C.

Production Example 1
Synthesis of amino group-containing adamantane derivative represented by formula (2-1)

In a reaction vessel (three-necked flask), 77.68 g (0.362 mol) of 3,3′-diaminobenzidine represented by the above formula (2-4) was placed, and 307 g of N, N-dimethylacetamide (DMAc) was added. After addition and dissolution, the temperature was kept at 0 ° C. or lower in 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 resulting precipitate was transferred to a reaction vessel equipped with a reflux tube, and 1.83 kg of tetrahydrofuran (THF) was added, followed by heating under reflux in a nitrogen atmosphere for washing 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. From the NMR spectrum data shown in FIG. 1 and the infrared absorption spectrum data shown in FIG. It was confirmed that the amino group-containing adamantane derivative represented by (2-4) 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
Synthesis of adamantane derivative containing ethoxycarbonylbutyl group represented by formula (1a-1)

In a reaction vessel (three-necked flask), 1.51 g (1.13 mmol) of an amino group-containing adamantane derivative represented by the above formula (2-1) and 1.07 g of an aldehyde compound represented by the above formula (B) ( 6.77 mmol), 13.5 g of N, N-dimethylacetamide (DMAc) was added and dissolved, and then the reaction vessel was oiled while introducing air into the reaction solution using a Teflon (registered trademark) tube. The bath was heated to maintain the liquid temperature at 90 ° C. and reacted for 6 hours. It was dripped at 150 ml of water in another container, and the slurry which consists of precipitation and a supernatant liquid was stirred for about 1 hour after completion | finish of dripping. The produced precipitate was filtered off, transferred again to the reaction vessel, washed with ethyl acetate, and the filtrate obtained by filtering the precipitate was dried in a vacuum dryer.
When the NMR spectrum of the product dried by the vacuum dryer was measured, it was confirmed from the NMR spectrum data that the compound represented by the above formula (1a-1) was formed.
[NMR spectral data]
¹ H-NMR (DMSO-d6) δ (ppm): 1.17 (12H <-CH ₃ >), 1.63 (8H <-CH _2- >), 1.83 (8H <-CH _2- >) _{), 2.35-2.37 (20H <-CH 2} ->), 2.85 (8H <-CH 2 ->), 4.06 (8H <-NH 2>), 7.48-8. 27 (40H <aromatic ring proton>), 12.26-12.98 (8H <-NH->)

Production Example 3
Synthesis of adamantane derivative containing ethoxycarbonylbutyl group and amino group represented by formula (3-1)

  In a reaction vessel (one-necked flask), 1.42 g (1.053 mmol) of the compound represented by the above formula (2-1) is added, and 12.7 g of N, N-dimethylacetamide (DMAc) is added and dissolved. After that, it was kept at 0 ° C. or lower with an ice bath. A solution prepared by dissolving 0.37 g (2.11 mmol) of ethyl = 5-formylpentanecarboxylate represented by the above formula (B) in 0.799 g of DMAc was added dropwise to the reaction vessel using a syringe. During dropping, care was taken that the liquid temperature in the reaction solution did not exceed 0 ° C. After completion of the dropwise addition, the reaction solution was heated at room temperature for 4.5 hours while introducing air into the reaction solution using a Teflon (registered trademark) tube, and then the reaction vessel was heated with an oil bath to keep the solution temperature at 90 ° C. The reaction was allowed for 5 hours. After completion of the reaction, the reaction solution was purged with nitrogen five times and shielded from light with aluminum foil to obtain a solution of an ethoxycarbonylbutyl group and amino group-containing adamantane derivative represented by the formula (3-1).

Production Example 4
Synthesis of an amino group-containing compound represented by the formula (1b-3)

In a reaction vessel (three-necked flask), 35.8 g (167 mmol) of 3,3′-diaminobenzidine represented by the above formula (2-4) was placed, and 143.0 g of N, N-dimethylacetamide (DMAc) was added. After addition and dissolution, the temperature was kept at 0 ° C. or lower in an ice bath. A solution prepared by dissolving 1.0 g (6.68 mmol) of octanedialdehyde in 50.4 g of DMAc was dropped into the reaction vessel at a rate of 2.5 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 10 ml of DMAc, and this was also dropped into the reaction vessel. After completion of the dropping, the reaction vessel was heated with an oil bath while introducing air into the reaction solution using a Teflon (registered trademark) tube, and the reaction temperature was kept at 60 ° C. for 4 hours. After completion of the reaction, the mixture was added dropwise to 2000 ml 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 stirring, the reaction solution was placed in a nitrogen atmosphere to prevent amine oxidation. The produced precipitate was separated by filtration, transferred again to the reaction vessel, 700 ml of water was added, and the mixture was heated under reflux for 30 minutes in a nitrogen atmosphere and washed with hot water. The precipitate was filtered off before the temperature dropped. This operation was repeated 7 times. Thereafter, the filtrate obtained by filtering the precipitate is transferred again to the reaction vessel, dissolved by adding methanol, dropped into water in another vessel, and the slurry consisting of the precipitate and the supernatant in a nitrogen atmosphere. Stir for about 1 hour. The filtrate obtained by filtering the precipitate was dried with a vacuum dryer.
When the NMR spectrum of the product dried by the vacuum dryer was measured, it was confirmed from the NMR spectrum data that the compound represented by the above formula (1b-3) was formed. The yield of the compound represented by the formula (1b-3) was 2.0 g, and the yield was 54%.
[NMR spectral data]
¹ H-NMR (DMSO-d6) δ (ppm): 1.22 (4H <—CH ₂ —>), 1.39 (4H <—CH ₂ —>), 1.77 (4H <—CH ₂ —) >), 2.49 (8H <-CH 2 ->), 2.79 (2H <-CH 2 ->), 4.50 (4H <-NH 2>), 6.56 (2H < aromatic protons >), 6.69 (2H <aromatic ring proton>), 6.84 (2H <aromatic ring proton>), 7.24 (2H <aromatic ring proton>), 7.35-7.54 (4H <aromatic Ring proton>), 12.09 (4H <-NH->)

Production Example 5
Synthesis of an amino group-containing compound represented by the formula (1b-4)

Into a reaction vessel (three-necked flask), 62.3 g (290 mmol) of 3,3′-diaminobenzidine represented by the above formula (2-4) was added, and 100 ml of N, N-dimethylacetamide (DMAc) was added. After dissolution, it was kept below 0 ° C. in an ice bath. A solution prepared by dissolving 1.26 g (14.5 mmol) of succinaldehyde in 100 ml of DMAc was dropped into the reaction vessel at a rate of 2 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 10 ml of DMAc, and this was also dropped into the reaction vessel. After completion of the dropping, the reaction vessel was heated with an oil bath while introducing air into the reaction solution using a Teflon (registered trademark) tube, and the reaction temperature was kept at 60 ° C. for 4 hours. After completion of the reaction, 100 ml of DMAc was distilled off from the reaction solution with an evaporator. The solution was added dropwise to 1000 ml 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 stirring, the reaction solution was placed in a nitrogen atmosphere to prevent amine oxidation. The produced precipitate was separated by filtration, transferred again to the reaction vessel, 700 ml of water was added, and the mixture was heated under reflux for 30 minutes in a nitrogen atmosphere and washed with hot water. The precipitate was filtered off before the temperature dropped. This operation was repeated 7 times. Thereafter, the filtrate obtained by filtering the precipitate is transferred again to the reaction vessel, dissolved by adding methanol, dropped into water in another vessel, and the slurry consisting of the precipitate and the supernatant in a nitrogen atmosphere. Stir for about 1 hour. The filtrate obtained by filtering the precipitate was dried with a vacuum dryer.
When the NMR spectrum of the product dried by the vacuum dryer was measured, it was confirmed from the NMR spectrum data that the compound represented by the above formula (1b-4) was formed. The yield of the compound represented by the formula 1b-4) was 801.2 mg, and the yield was 46%.
[NMR spectral data]
¹ H-NMR (DMSO-d6) δ (ppm): 2.80 (4H <—CH ₂ —>), 4.51 (8H <—NH ₂ >), 6.57 (2H <aromatic ring proton>) 6.70 (2H <aromatic ring proton>), 6.85 (2H <aromatic ring proton>), 7.24 (2H <aromatic ring proton>), 7.35-7.55 (4H <aromatic ring proton) >), 12.08 (2H <-NH->)

Production Example 6
Synthesis of an amino group- and hydroxyl group-containing compound represented by the formula (1b-5)

In a container (conical flask), 1.5 g (7.11 mmol) of hexane-1,6-dicarboxylic acid chloride was added, and 307 g of N, N-dimethylacetamide (DMAc) was added and dissolved, and then a dry ice / methanol bath. At -20 ° C. Similarly, 30.7 g (142 mmol) of 3,3′-dihydroxybenzidine represented by the above formula (2-4) is placed in a container (erlenmeyer flask), and 307 g of N, N-dimethylacetamide (DMAc) is added. After addition and dissolution, the mixture was cooled to −20 ° C. in a dry ice / methanol bath. The above two liquids were mixed at a constant rate using a syringe into a reaction vessel kept at −18 ° C. or lower with a cooling device, and stirred for 1.5 hours. After completion of the reaction, the solvent was distilled off using an evaporator until the solid content concentration became 15% by weight. The solution was added dropwise to 1000 ml of methanol 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 flask, and DMAc was added to the obtained filtrate to dissolve it so that the solid content concentration became 15% by weight. The solution was added dropwise to 1000 ml of methanol 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 formed precipitate was filtered off. This was repeated 7 times. The solid content finally obtained was dried with a vacuum dryer.
When the NMR spectrum of the product dried by the vacuum dryer was measured, it was confirmed from the NMR spectrum data that the compound represented by the above formula (1b-5) was formed.
[NMR spectral data]
¹ H-NMR (DMSO-d6) δ (ppm): 1.35 (4H <—CH ₂ —>), 2.40 (4H <—CH ₂ —>), 2.50 (4H <—CH ₂ —) >), 4.63 (4H <-NH 2>), 6.57-7.05 (10H < aromatic protons>), 7.64 (2H <aromatic protons>), 9.10-9.78 (6H)

Comparative Example 1 [Production of Film from (2-1) and (2-2) (Membrane 1)]
In a well-dried container (an eggplant-shaped flask), 464 mg (0.752 mmol) of the carboxylic acid compound represented by the formula (2-2) and 1330 mg (0. 752 mmol), 6.73 g of N, N-dimethylacetamide (DMAc) and 6.73 g of 1,3-dimethyl-2-imidazolidinone (DMI) were added and dissolved, and then a vacuum pump was used while stirring. Then, deaeration and nitrogen substitution were repeated three times. After shielding from light and stirring for 1 hour, stirring was stopped and the mixture was allowed to stand overnight. This solution was filtered through 0.2 μm and 0.1 μm PTFE filter paper, and then applied onto a silicon substrate under the conditions of 1000 rpm / 20 sec → 3000 rpm / 20 sec. Immediately after that, the film was fired under the conditions of 50 ° C. → 250 ° C. (30 min) → 400 ° C. (30 min) to obtain a film 1. The film thickness of the film 1 was 170.0 nm.
[Infrared absorption spectrum data (cm ⁻¹ )]
3419 (N-H <stretching vibration>), 2933 (-CH ₂ - <stretching vibration>), 1623 (-C = N-<stretching vibration>), 1420-1520 (aromatic <plane vibration>), 1280 (Aromatic —NH ₂ <stretching vibration>), 807 (C—H <out-of-plane variable vibration>)

Example 1 [Preparation of film from (2-2) and (1b-3) (film 2)]
In a well-dried container (eggplant type flask), 395 mg (0.641 mmol) of the carboxylic acid compound represented by (2-2) and 680 mg (1.28 mmol) of the amine compound represented by (1b-3) After adding 3.49 g of N, N-dimethylacetamide (DMAc) and 3.50 g of 1,3-dimethyl-2-imidazolidinone (DMI) and dissolving, it was removed using a vacuum pump while stirring. Ki and nitrogen substitution were repeated three times. After shielding from light and stirring for 1 hour, stirring was stopped and the mixture was allowed to stand overnight. This solution was filtered through 0.2 μm and 0.1 μm PTFE filter paper, and then applied onto a silicon substrate under the conditions of 1000 rpm / 20 sec → 3000 rpm / 20 sec. Immediately thereafter, the film was fired under the conditions of 50 ° C. → 250 ° C. (30 min) → 400 ° C. (30 min) to obtain a film 2. The film thickness of the film 2 was 214.7 nm.
[Infrared absorption spectrum data (cm ⁻¹ )]
3445 (N-H <stretching vibration>), 2930 (-CH ₂ - <stretching vibration>), 1620 (-C = N-<stretching vibration>), 1420-1520 (aromatic <plane vibration>), 1280 (Aromatic —NH ₂ <stretching vibration>), 806 (C—H <out-of-plane variable vibration>)

Example 2 [Production of film from (1b-1) and (2-1) (film 3)]
In a well-dried container (an eggplant-shaped flask), 0.401 g (1.81 mmol) of 1,4-phenylenedipropionic acid represented by (1b-1) and (2 -1) 1.20 mg (0.904 mmol) of the amine compound, N, N-dimethylacetamide (DMAc) 5.88 g and 1,3-dimethyl-2-imidazolidinone (DMI) 5.88 g Then, deaeration and nitrogen substitution were repeated 3 times using a vacuum pump while stirring. After shielding from light and stirring for 1 hour, stirring was stopped and the mixture was allowed to stand overnight. This solution was filtered through 0.2 μm and 0.1 μm PTFE filter paper, and then applied onto a silicon substrate under the conditions of 1000 rpm / 20 sec → 3000 rpm / 20 sec. Immediately after that, the film was fired under the conditions of 50 ° C. → 250 ° C. (30 min) → 400 ° C. (30 min) to obtain a film 3. The film thickness of the film 3 was 217.2 nm.
[Infrared absorption spectrum data (cm ⁻¹ )]
3420 (N-H <stretching vibration>), 2933 (-CH ₂ - <stretching vibration>), 1620 (-C = N-<stretching vibration>), 1420-1520 (aromatic <plane vibration>), 1260 (Aromatic-NH ₂ <stretching vibration>), 810 (C—H <out-of-plane variable vibration>)

Example 3 [Preparation of film from (1a-1) and (2-1) (film 4)]
In a well-dried container (eggplant type flask), 1.00 g (0.531 mmol) of the ester compound represented by (1a-1) and 0.707 g (0) of the amine compound represented by (2-1) above. 531 mmol), 7.2 g of N, N-dimethylacetamide (DMAc) and 7.1 g of 1,3-dimethyl-2-imidazolidinone (DMI) were added and dissolved, and then a vacuum pump was used while stirring. Degassing and nitrogen replacement were repeated 3 times. After shielding from light and stirring for 1 hour, stirring was stopped and the mixture was allowed to stand overnight. This solution was filtered through 0.2 μm and 0.1 μm PTFE filter paper, and then applied onto a silicon substrate under the conditions of 1000 rpm / 20 sec → 3000 rpm / 20 sec. Immediately after that, the film 4 was fired under the conditions of 50 ° C. → 250 ° C. (30 min) → 400 ° C. (30 min) to obtain a film 4. The thickness of the film 4 was 211.1 nm.
[Infrared absorption spectrum data (cm ⁻¹ )]
3419 (N-H <stretching vibration>), 2931 (-CH ₂ - <stretching vibration>), 1623 (-C = N-<stretching vibration>), 1420-1520 (aromatic <plane vibration>), 1282 (Aromatic —NH ₂ <stretching vibration>), 805 (C—H <out-of-plane variable vibration>)

Example 4 [Production of film from (3-1) (film 5)]
The solution of the ethoxycarbonylbutyl group and amino group-containing adamantane derivative represented by formula (3-1) obtained in Production Example 3 was filtered through 0.2 μm and 0.1 μm PTFE filter paper, and then 1000 rpm / 20 sec → 3000 rpm / 20 sec. It apply | coated on the silicon substrate on condition. Immediately after that, the film 5 was baked under the conditions of 50 ° C. → 250 ° C. (30 min) → 400 ° C. (30 min). The film thickness of the film 5 was 114.7 nm.
[Infrared absorption spectrum data (cm ⁻¹ )]
3419 (N-H <stretching vibration>), 2929 (-CH ₂ - <stretching vibration>), 1620 (-C = N-<stretching vibration>), 1420-1520 (aromatic <plane vibration>), 1280 (Aromatic-NH ₂ <stretching vibration>), 810 (C—H <out-of-plane variable vibration>)

Evaluation test 1
About the film | membrane obtained in Examples 1-4 and Comparative Example 1, the dielectric constant was measured in arbitrary 12 places in the same film | membrane. The results are shown in FIGS. The horizontal axis represents the number of the measurement location, and the vertical axis represents the relative dielectric constant value. As is clear from the figure, the film of Comparative Example 1 shows a large variation in relative dielectric constant depending on the measurement location, but the film obtained in the example has a small variation in relative dielectric constant depending on the measurement location and is a homogeneous film. Met.

Evaluation test 2
About the film | membrane obtained in Example 1 and Comparative Example 1, the leakage current was measured. The result is shown in FIG. The horizontal axis represents the applied electric field E (V / cm), and the vertical axis represents the leakage current (A / cm ² ). As is clear from the figure, the film of Example 1 was superior to the film of Comparative Example 1 in insulation.

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. 6 is a graph showing variations in relative permittivity within the same film obtained in Example 1 and Comparative Example 1. It is a graph which shows the variation in a dielectric constant within the same film | membrane of the film | membrane obtained in Example 2, 3 and 4. It is a graph which shows the relationship between the applied electric field and leakage current of the film | membrane obtained in Example 1 and Comparative Example 1.

Claims (22)

Each compound has two or more functional groups or functional group groups in the molecule, and is polymerized by bonding between the functional group or functional group group of one compound and the functional group or functional group group of the other compound. Two compounds A and B capable of forming a polymer having a pore structure, and / or two or more functional groups or functional groups in the molecule, one functional group or functional groups And an insulating film forming material containing Compound C, which can be polymerized by bonding with other functional groups or functional groups to form a polymer having a pore structure, which includes Compound A, Compound B, and Compound C. Satisfies the following condition (i) or (ii).
(I) At least one of Compound A and Compound B has a bridged alicyclic skeleton or an aromatic ring skeleton as a central skeleton, and at least one of Compound A and Compound B is a central skeleton and the functional group or functional group group Having a heat-resistant skeleton composed of a divalent organic group containing an aromatic ring, and at least one of compound A and compound B having 2 to 20 atoms in total containing at least an alkylene group or an ether bond in the molecule A pair of functional groups or functional groups having a flexible unit composed of an organic group and capable of forming a heterocyclic ring by reacting the functional group or functional group group of compound A and the functional group or functional group group of compound B with each other. (Ii) Compound C has a bridged alicyclic skeleton or an aromatic ring skeleton as a central skeleton, and is a group that includes an ethynyl group that may have a substituent. Said one officer A heat-resistant skeleton composed of a divalent organic group containing an aromatic ring between the group or functional group and / or between the central skeleton and another functional group or functional group, A flexible unit comprising an organic group having 2 to 20 atoms in total containing at least an alkylene group or an ether bond between the functional group or the functional group of and / or between the central skeleton and another functional group or the functional group. And one functional group or functional group group of compound C and another functional group or functional group group are a pair of functional groups or functional groups capable of reacting with each other to form a heterocyclic ring, Or a group containing an ethynyl group which may have a substituent. At least one of compound A and compound B, or a bridged alicyclic skeleton or aromatic ring skeleton as a central skeleton possessed by compound C is a ring selected from the following formula, or two or more of these 2. The insulating film forming material according to claim 1, wherein the insulating film forming material is a bonded ring.

(Wherein r represents an integer of 0 to 5) 2. The heat-resistant skeleton composed of a divalent organic group containing an aromatic ring included in at least one of Compound A and Compound B or Compound C is a group selected from the following formulas or a group in which two or more of these are bonded. The insulating film forming material as described.

(In the formula, s represents an integer of 0 to 5) The flexible unit comprising an organic group having 2 to 20 atoms in total containing at least one of the compound A and the compound B or the alkylene group or ether bond of the compound C is a flexible unit comprising a group selected from the following formulae: 2. The insulating film forming material according to 1.

(In the formula, t represents an integer of 1 to 19, u represents an integer of 1 to 10, v represents an integer of 1 to 3, w represents an integer of 1 to 16, and x represents 1 to 14) Y and z are each an integer of 0 to 6, provided that y and z are not 0 at the same time.   A heterocyclic ring formed by the reaction of the functional group or functional group of compound A and the functional group or functional group of compound B with each other, or one functional group or functional group of compound C and another functional group or functional group The insulating film forming material according to claim 1, wherein the heterocyclic ring formed by reacting with each other is a benzimidazole ring, a benzoxazole ring, or a benzthiazole ring. The insulating film forming material according to claim 1, wherein the compound A, the compound B, and the compound C satisfy the following condition (iii) or (iv).
(Iii) Compound A is represented by the following formula (1a)

[Wherein, X ¹ represents a divalent to tetravalent bridged alicyclic group or an aromatic cyclic group. Y ^1a and Y ^1b are the same or different and represent a single bond, a divalent aromatic hydrocarbon group, a divalent aromatic heterocyclic group, or a precursor of a divalent aromatic heterocyclic group. And a divalent group in which two or more of these groups are bonded. W ¹ represents a flexible unit composed of a divalent group having 2 to 20 atoms and containing at least an alkylene group or an ether bond. Z ¹ is a group containing a functional group or a functional group capable of reacting with Z ² in the following formula (2) to form a heterocyclic ring, or an ethynyl group optionally having a substituent (provided that the formula (2) In which Z ² is a group containing an ethynyl group which may have a substituent. R ¹ represents a hydrogen atom or a hydrocarbon group. n1 shows the integer of 2-4, n2 shows the integer of 0-2. n1 + n2 = 2-4. A plurality of Y ^1a , Y ^1b , W ¹ , Z ¹ in the molecule, and R ¹ in the case where a plurality exist may be the same or different.]
Or a compound represented by the following formula (1b)

[Wherein Y ¹ represents a single bond, a divalent aromatic hydrocarbon group, a divalent aromatic heterocyclic group, a divalent group corresponding to a precursor of a divalent aromatic heterocyclic group, Or the bivalent group which these groups couple | bonded two or more is shown. W represents a flexible unit composed of a divalent to tetravalent group having 2 to 20 atoms and containing at least an alkylene group or an ether bond. Z ¹ is a group containing a functional group or a functional group capable of reacting with Z ² in the following formula (2) to form a heterocyclic ring, or an ethynyl group optionally having a substituent (provided that the formula (2) In which Z ² is a group containing an ethynyl group which may have a substituent. n shows the integer of 2-4. Plural Y ¹ and Z ¹ in the molecule may be the same or different.
The compound B is represented by the following formula (2):

[Wherein, X ² represents a divalent to tetravalent bridged alicyclic group or an aromatic cyclic group. Y ^2a and Y ^2b are the same or different and represent a single bond, a divalent aromatic hydrocarbon group, a divalent aromatic heterocyclic group, or a precursor of a divalent aromatic heterocyclic group. And a divalent group in which two or more of these groups are bonded. W ² represents a flexible unit composed of a divalent group having 2 to 20 atoms in total containing at least an alkylene group or an ether bond. Z ² represents a functional group or a group of functional groups that can form a heterocyclic ring by reacting with Z ¹ in the formula (1a) or (1b), or a group containing an ethynyl group which may have a substituent (provided that Z ¹ in formula (1a) or (1b) is limited to a group containing an ethynyl group which may have a substituent. R ² represents a hydrogen atom or a hydrocarbon group. m1 represents an integer of 2 to 4, and m2 represents an integer of 0 to 2. m1 + m2 = 2-4. i represents 0 or 1, and k represents 0 or 1. A plurality of Y ^2a , Y ^2b , W ² , Z ² in the molecule, and R ² in the case where a plurality exist may be the same or different.]
(Iv) Compound C is represented by the following formula (3):

[Wherein, X ¹ represents a divalent to tetravalent bridged alicyclic group or an aromatic cyclic group. Y ^1a , Y ^1b , Y ^2a and Y ^2b are the same or different and are each a single bond, a divalent aromatic hydrocarbon group, a divalent aromatic heterocyclic group or a divalent aromatic heterocyclic group. A divalent group corresponding to a precursor or a divalent group in which two or more of these groups are bonded to each other is shown. W ¹ and W ² are the same or different and each represents a flexible unit comprising a divalent group having 2 to 20 atoms and containing at least an alkylene group or an ether bond. Z ¹ and Z ² are a functional group or a group of functional groups that can form a heterocycle by reacting with each other, or both Z ¹ and Z ² may have a substituent. A substituent containing a group is shown. R ¹ represents a hydrogen atom or a hydrocarbon group. k represents 0 or 1. p1 and p2 each represent an integer of 1 to 3, and p3 represents an integer of 0 to 2. p1 + p2 + p3 = 2-4. Y ^1a , Y ^1b , Y ^2a , Y ^2b , W ¹ , W ² , Z ¹ , Z ² , R ¹ in the case where there are a plurality in the molecule may be the same or different.
Is a compound represented by In formula (1a), X ¹ in formula (3), a divalent to tetravalent bridged alicyclic group or a bridged alicyclic ring related to an aromatic cyclic group, a ring in which the aromatic ring is selected from the following formulas, or The insulating film forming material according to claim 6, which is a ring in which two or more are bonded.

(Wherein r represents an integer of 0 to 5) Y ^1a , Y ^1b , Y ¹ , Y ^2a , Y ^{2b in} formula (1a), formula (1b), formula (2), and formula (3) are a single bond or a group selected from the following formulas, or The insulating film forming material according to claim 6, which is a group in which two or more are bonded.

(In the formula, s represents an integer of 0 to 5) The insulating film forming material according to claim 6, wherein W ¹ , W, and W ^{2 in} Formula (1a), Formula (1b), Formula (2), and Formula (3) are flexible units composed of groups selected from the following formulas: .

(In the formula, t represents an integer of 1 to 19, u represents an integer of 1 to 10, v represents an integer of 1 to 3, w represents an integer of 1 to 16, and x represents 1 to 14) Y and z are each an integer of 0 to 6, provided that y and z are not 0 at the same time. A heterocycle formed by Z ¹ in formula (1a) or formula (1b) and Z ² in formula (2), a heterocycle formed by Z ¹ in formula (3) and Z ² in formula (3) The material for forming an insulating film according to claim 6, wherein is a benzimidazole ring, a benzoxazole ring or a benzthiazole ring. ^One of Z ¹ in formula (1a) or formula (1b) and Z ² in formula (2), or Z ¹ in formula (3) and Z ² in formula (3) is a carboxyl group, a substituted oxycarbonyl group, formyl Group, a haloformyl group or a group containing an optionally substituted ethynyl group, the other being 3,4-diaminophenyl group, 3-amino-4-hydroxyphenyl group, 4-amino-3-hydroxyphenyl Group, a 3-amino-4-mercaptophenyl group, a 4-amino-3-mercaptophenyl group or a group containing an ethynyl group which may have a substituent (provided that one has a substituent) The material for forming an insulating film according to claim 6, wherein when the group is a group containing an ethynyl group, the other is a group containing an ethynyl group which may have a substituent.   The insulating film forming material according to any one of claims 1 to 11, which is a solution in which the compound A and the compound B and / or the compound C are dissolved in an organic solvent.   A polymer having a pore structure obtained by subjecting the insulating film-forming material according to any one of claims 1 to 12 to a polymerization reaction.   An insulating film made of a polymer having a pore structure according to claim 13.   A method for producing an insulating film, comprising: applying an insulating film forming material according to claim 12 on a base material; and subjecting the material to a polymerization reaction to form an insulating film made of a polymer having a pore structure. Following formula (7)

[Wherein, X ¹ represents a divalent to tetravalent aromatic or non-aromatic cyclic group. Y ^1a and Y ^1b are the same or different and represent a single bond, a divalent aromatic hydrocarbon group, a divalent aromatic heterocyclic group, or a precursor of a divalent aromatic heterocyclic group. And a divalent group in which two or more of these groups are bonded. However, at least one of Y ^1a and Y ^1b is a group containing a divalent aromatic heterocyclic group or a divalent group corresponding to a precursor of a divalent aromatic heterocyclic group. W ¹ represents a flexible unit composed of a divalent group having 2 to 20 atoms in total containing at least an alkylene group or an ether bond. Z ¹ represents a carboxyl group, a substituted oxycarbonyl group, a formyl group, a haloformyl group, a group containing an optionally substituted ethynyl group, a 3,4-diaminophenyl group, a 3-amino-4-hydroxyphenyl group, A 4-amino-3-hydroxyphenyl group, a 3-amino-4-mercaptophenyl group or a 4-amino-3-mercaptophenyl group is shown. R ¹ represents a hydrogen atom or a hydrocarbon group. n1 shows the integer of 2-4, n2 shows the integer of 0-2. n1 + n2 = 2-4. A plurality of Y ^1a , Y ^1b , W ¹ , Z ¹ in the molecule, and R ¹ in the case where a plurality exist may be the same or different.]
A polymerizable compound represented by the formula: At least one of Y ^1a and Y ^{1b corresponds} to a divalent aromatic heterocyclic group containing a benzimidazole ring, benzoxazole ring or benzthiazole ring, or a precursor of the divalent aromatic heterocyclic group. The polymerizable compound according to claim 16, which is a divalent group. Following formula (8)

[Wherein Y ¹ represents a divalent aromatic heterocyclic group or a divalent group corresponding to a precursor of a divalent aromatic heterocyclic group. W represents a flexible unit composed of a divalent to tetravalent group having 2 to 20 atoms and containing at least an alkylene group or an ether bond. Z ¹ represents a carboxyl group, a substituted oxycarbonyl group, a formyl group, a haloformyl group, a group containing an optionally substituted ethynyl group, a 3,4-diaminophenyl group, a 3-amino-4-hydroxyphenyl group, A 4-amino-3-hydroxyphenyl group, a 3-amino-4-mercaptophenyl group or a 4-amino-3-mercaptophenyl group is shown. n shows the integer of 2-4. Plural Y ¹ and Z ¹ in the molecule may be the same or different.
A polymerizable compound represented by the formula: Y ¹ is a divalent aromatic heterocyclic group containing a benzimidazole ring, benzoxazole ring or benzthiazole ring, or a divalent group corresponding to a precursor of the divalent aromatic heterocyclic group. The polymerizable compound according to claim 18. Following formula (9)

[Wherein, X ¹ represents a divalent to tetravalent organic group. Y ^1a , Y ^1b , Y ^2a and Y ^2b are the same or different and are each a single bond, a divalent aromatic hydrocarbon group, a divalent aromatic heterocyclic group or a divalent aromatic heterocyclic group. A divalent group corresponding to a precursor or a divalent group in which two or more of these groups are bonded to each other is shown. However, at least one of Y ^1a and Y ^1b is a group containing a divalent aromatic heterocyclic group or a divalent group corresponding to a precursor of a divalent aromatic heterocyclic group. W ¹ and W ² are the same or different and each represents a flexible unit comprising a divalent group having 2 to 20 atoms and containing at least an alkylene group or an ether bond. Z ¹ and Z ² are each a carboxyl group, a substituted oxycarbonyl group, a formyl group, a haloformyl group, a group containing an optionally substituted ethynyl group, 3,4-diaminophenyl group, 3-amino- 4-hydroxyphenyl group, 4-amino-3-hydroxyphenyl group, 3-amino-4-mercaptophenyl group or 4-amino-3-mercaptophenyl group is shown. R ¹ represents a hydrogen atom or a hydrocarbon group. k represents 0 or 1. p1 and p2 each represent an integer of 1 to 3, and p3 represents an integer of 0 to 2. p1 + p2 + p3 = 2-4. Y ^1a , Y ^1b , Y ^2a , Y ^2b , W ¹ , W ² , Z ¹ , Z ² , R ¹ in the case where there are a plurality in the molecule may be the same or different.
A polymerizable compound represented by the formula: At least one of Y ^1a and Y ^{1b corresponds} to a divalent aromatic heterocyclic group containing a benzimidazole ring, benzoxazole ring or benzthiazole ring, or a precursor of the divalent aromatic heterocyclic group. The polymerizable compound according to claim 20, which is a divalent group. At least one of Y ^2a and Y ^{2b corresponds} to a divalent aromatic heterocyclic group containing a benzimidazole ring, benzoxazole ring or benzthiazole ring, or a precursor of the divalent aromatic heterocyclic group. The polymerizable compound according to claim 20 or 21, which is a divalent group.

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