JP2005272352A - Cyclic aminophenol compound, cyclic thermoset resin, method for producing the same, material for insulation film, coating varnish for insulation film, and insulation film and semiconductor device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a compound as a material for an insulation film having excellent heat resistance, water absorption, mechanical characteristics and the like, and capable of being formed into a low dielectric film. <P>SOLUTION: The compound is a cyclic aminophenol compound having an aromatic group with a group containing an aminophenol structure in the main chain. For example, the compound is exemplified by the compound of formula (1) (wherein, Ar is an aromatic group; X<SB>1</SB>and X<SB>2</SB>are each a hydrogen atom, an aliphatic group, an aromatic group or a sulfonyl group; m is an integer of ≥3 and ≤20; and n is an integer of ≥1 and ≤3). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a cyclic aminophenol compound, a cyclic thermosetting resin, a production method thereof, an insulating film material using the cyclic aminophenol compound, an insulating film coating varnish, an insulating film using the same, and a semiconductor device.

  Cyclic compounds such as calixarene form an inclusion compound and are expected as adsorbents for heavy metal ions in water, and attempts have been made to synthesize derivatives for the purpose of improving solubility in water. As one of means for using such a calixarene derivative as a functional material, there has been an example in which film formation of calixarene and its derivative has been studied (for example, see Patent Document 1). However, cyclic compounds such as calixarene are inferior in heat resistance and cannot be used as thermosetting resins. Moreover, the example which synthesize | combined the thermosetting resin using such a cyclic compound is not yet known.

On the other hand, in semiconductor materials, inorganic materials, organic materials, and the like are used in various portions according to required characteristics. For example, as an interlayer insulating film for a semiconductor, an inorganic oxide film such as silicon dioxide produced by a chemical vapor deposition method is used. However, with the recent increase in speed and performance of semiconductors, the inorganic oxide film as described above has a problem that the relative dielectric constant is high. As one of the improvement means, application of an organic material has been studied (for example, refer to Patent Document 2).
As an organic material for semiconductor use, there is a polybenzoxazole resin excellent in heat resistance, water absorption, electrical characteristics, mechanical characteristics, and the like, and application to various fields has been attempted. For example, one having a structure consisting of 4,4′-diamino-3,3′-dihydroxybiphenyl and terephthalic acid, a structure consisting of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and terephthalic acid There are polybenzoxazole resins and the like.

However, in advanced fields where further improvements in strict heat resistance, water absorption, electrical characteristics, mechanical characteristics, etc. are required, no material that satisfies all of these requirements has yet been obtained. That is, although the mechanical properties of the material exhibiting excellent heat resistance are not sufficient, the electrical properties are improved by introducing fluorine, but there is a problem that the heat resistance is reduced. In particular, when an organic material is applied as an interlayer insulating film for semiconductors, heat resistance, water absorption, and mechanical properties comparable to those of inorganic materials are required, and further lower dielectric constant is required.
JP-A-4-15232 US Pat. No. 5,776,990

  Under such circumstances, the present invention has an excellent heat resistance and a cyclic aminophenol compound that can be converted into a cyclic thermosetting resin, and is converted from the cyclic aminophenol, resulting in heat resistance, water absorption, mechanical properties, and electricity. It aims at providing the cyclic | annular thermosetting resin which is excellent in a characteristic, and its manufacturing method. Furthermore, by using these materials, it is possible to achieve both heat resistance, water absorption, mechanical properties, and the like, and particularly excellent insulating materials, insulating coating materials including these, insulating films containing them, insulating films using these, and insulating films It is an object to provide a semiconductor device having the following.

  As a result of intensive studies to achieve the above object, the present inventors have found a cyclic compound having a thermosetting group and a hollow structure in the compound, and further using this as a material for an insulating film. Thus, it has been found that the object can be achieved, and the present invention has been completed based on this finding.

That is, the present invention
1. A cyclic aminophenol compound having an aromatic group having a group containing an aminophenol structure in the main chain;
2. The cyclic aminophenol compound according to item 1, wherein the group containing an aminophenol structure is an o-aminohydroxyphenoxy group,
3. The cyclic aminophenol compound according to item 2, wherein the cyclic aminophenol compound has a structure represented by the general formula (1),

（式中のＡｒは芳香族基を示す。式中のＸ₁およびＸ₂は、それぞれ独立して、水素原子、脂肪族基、芳香族基またはスルホニル基の中から選ばれる少なくとも１種の基で構成される基であり、互いに同一であっても異なっていても良い。式中のｍは、３以上、２０以下の整数を示す。式中のｎは、１以上、３以下の整数を示す。）

(In the formula, Ar represents an aromatic group. X ₁ and X ₂ in the formula are each independently at least one group selected from a hydrogen atom, an aliphatic group, an aromatic group or a sulfonyl group. In the formula, m represents an integer of 3 or more and 20 or less, and n in the formula represents an integer of 1 or more and 3 or less. Show.)

4). The cyclic aminophenol compound according to item 3, wherein the cyclic aminophenol compound has a group selected from the group represented by the formula (2) as X ₁ and X ₂ in the general formula (1). ,

（式中のＲ₁およびＲ₂は、それぞれ独立して、式（３）で表される基の中から選ばれる基を示し、互いに同一であっても異なっていても良い。また、式中の水素原子は、脂肪族基、芳香族基およびフッ素原子の中から選ばれる、少なくとも１種の基で置換されていても良い。）

(R ₁ and R ₂ in the formula each independently represent a group selected from the groups represented by formula (3), and may be the same or different from each other. The hydrogen atom may be substituted with at least one group selected from an aliphatic group, an aromatic group and a fluorine atom.)

（式中の水素原子は、脂肪族基、芳香族基およびフッ素原子の中から選ばれる、少なくとも１種の基で置換されていても良い。）

(The hydrogen atom in the formula may be substituted with at least one group selected from an aliphatic group, an aromatic group and a fluorine atom.)

5). The cyclic aminophenol compound according to item 4, which is a calix resorcalene derivative having at least one of a methyl group and a phenyl group as X ₁ and X ₂ in the general formula (1),
6). The cyclic aminophenol compound according to item 4, wherein the cyclic aminophenol compound is a calix [4] arene derivative or calix [6] arene derivative having one or more t-butyl groups as Ar in the general formula (1). Phenolic compounds,
7). A cyclic thermosetting resin having an aromatic group in the main chain having a substituent containing an amidephenol structure having an organic group on the carbon of the amide bond;
8). The cyclic thermosetting resin according to item 7, wherein the substituent containing the amidophenol structure is an o-amidohydroxyphenoxy group,
9. The cyclic thermosetting resin according to item 7 or 8, wherein the cyclic thermosetting resin has a structure represented by the general formula (4),

（式中のＡｒは芳香族基を示す。式中のＸ₁およびＸ₂は、それぞれ独立して、水素原子、脂肪族基、芳香族基またはスルホニル基の中から選ばれる少なくとも１種の基で構成される基であり、互いに同一であっても異なっていても良い。式中のＲは有機基を示す。式中のｍは、３以上、２０以下の整数を示す。式中のｎは、１以上、３以下の整数を示す。）

(In the formula, Ar represents an aromatic group. X ₁ and X ₂ in the formula are each independently at least one group selected from a hydrogen atom, an aliphatic group, an aromatic group or a sulfonyl group. And R may be the same as or different from each other, R in the formula represents an organic group, m represents an integer of 3 to 20, and n in the formula Represents an integer of 1 to 3.

10. The cyclic thermosetting resin according to any one of Items 7 to 9, wherein the cyclic thermosetting resin has a group containing an acetylene group as R in the general formula (4),
11. The cyclic thermosetting resin according to item 10, wherein the cyclic thermosetting resin has a structure represented by the general formula (5),

（式中のＡｒは芳香族基を示す。式中のＸ₁およびＸ₂は、それぞれ独立して、水素原子、脂肪族基、芳香族基またはスルホニル基の中から選ばれる少なくとも１種の基で構成される基であり、互いに同一であっても異なっていても良い。式中Ｙは、アセチレン基を含む有機基を示す。式中のｍは、３以上、２０以下の整数を示す。式中のｎは、１以上、３以下の整数を示す。式中ｐは、１以上、５以下の整数を示す。）

(In the formula, Ar represents an aromatic group. X ₁ and X ₂ in the formula are each independently at least one group selected from a hydrogen atom, an aliphatic group, an aromatic group or a sulfonyl group. In which Y represents an organic group containing an acetylene group, and m in the formula represents an integer of 3 or more and 20 or less. N in the formula represents an integer of 1 to 3. In the formula, p represents an integer of 1 to 5.

12 The cyclic thermosetting resin according to item 11, wherein the cyclic thermosetting resin has a structure represented by the general formula (6),

（式中のＡｒは芳香族基を示す。式中のＸ₁およびＸ₂は、それぞれ独立して、水素原子、脂肪族基、芳香族基またはスルホニル基の中から選ばれる少なくとも１種の基で構成される基であり、互いに同一であっても異なっていても良い。式中Ｚは、水素基または有機基を示す。式中のｍは、３以上、２０以下の整数を示す。式中のｎは、１以上、３以下の整数を示す。式中ｐは、１以上、５以下の整数を示す。）

(In the formula, Ar represents an aromatic group. X ₁ and X ₂ in the formula are each independently at least one group selected from a hydrogen atom, an aliphatic group, an aromatic group or a sulfonyl group. And Z may be the same as or different from each other, wherein Z represents a hydrogen group or an organic group, and m represents an integer of 3 or more and 20 or less. (In the formula, n represents an integer of 1 to 3. In the formula, p represents an integer of 1 to 5.)

13. The cyclic thermosetting resin has a group selected from the group represented by the formula (2) as X ₁ and X ₂ in the general formula (4), the general formula (5), or the general formula (6). The cyclic thermosetting resin according to any one of Items 9 to 12, which is

（式中のＲ₁およびＲ₂は、それぞれ独立して、式（３）で表される基の中から選ばれる基を示し、互いに同一であっても異なっていても良い。また、式中の水素原子は、脂肪族基、芳香族基およびフッ素原子の中から選ばれる、少なくとも１種の基で置換されていても良い。）

(R ₁ and R ₂ in the formula each independently represent a group selected from the groups represented by formula (3), and may be the same or different from each other. The hydrogen atom may be substituted with at least one group selected from an aliphatic group, an aromatic group and a fluorine atom.)

（式中の水素原子は、脂肪族基、芳香族基およびフッ素原子の中から選ばれる、少なくとも１種の基で置換されていても良い。）

(The hydrogen atom in the formula may be substituted with at least one group selected from an aliphatic group, an aromatic group and a fluorine atom.)

14 A cyclic compound having a structure represented by the general formula (1) is condensed with a carboxylic acid halogen compound or a carboxylic acid ester product to form an amide bond, which is represented by the general formula (4) A method for producing a cyclic thermosetting resin having a structure;

（式中のＡｒは芳香族基を示す。式中のＸ₁およびＸ₂は、それぞれ独立して、水素原子、脂肪族基、芳香族基またはスルホニル基の中から選ばれる少なくとも１種の基で構成される基であり、互いに同一であっても異なっていても良い。式中のｍは、３以上、２０以下の整数を示す。式中のｎは、１以上、３以下の整数を示す。）

(In the formula, Ar represents an aromatic group. X ₁ and X ₂ in the formula are each independently at least one group selected from a hydrogen atom, an aliphatic group, an aromatic group or a sulfonyl group. In the formula, m represents an integer of 3 or more and 20 or less, and n in the formula represents an integer of 1 or more and 3 or less. Show.)

（式中のＡｒは芳香族基を示す。式中のＸ₁およびＸ₂は、それぞれ独立して、水素原子、脂肪族基、芳香族基またはスルホニル基の中から選ばれる少なくとも１種の基で構成される基であり、互いに同一であっても異なっていても良い。式中のＲは有機基を示す。式中のｍは、３以上、２０以下の整数を示す。式中のｎは、１以上、３以下の整数を示す。）

(In the formula, Ar represents an aromatic group. X ₁ and X ₂ in the formula are each independently at least one group selected from a hydrogen atom, an aliphatic group, an aromatic group or a sulfonyl group. And R may be the same as or different from each other, R in the formula represents an organic group, m represents an integer of 3 to 20, and n in the formula Represents an integer of 1 to 3.

15. An insulating film material comprising the cyclic thermosetting resin according to any one of Items 7 to 13,
16. An insulating film coating varnish comprising the insulating film material according to Item 15 and an organic solvent capable of dissolving or dispersing the insulating film material,
17. A resin layer mainly comprising polybenzoxazole obtained by subjecting the insulating film material according to Item 15 or the insulating film coating varnish according to Item 16 to a condensation reaction and a crosslinking reaction by heat treatment. An insulating film comprising:
18. The insulating film according to item 17, which is used as an interlayer insulating film for a multilayer wiring of a semiconductor,
19. The insulating film according to item 17, which is used as a semiconductor surface protective film,
20. A semiconductor device comprising: an interlayer insulating film for multilayer wiring comprising the insulating film according to Item 18; and / or a surface protective layer comprising the insulating film according to Item 19.
Is to provide.

  ADVANTAGE OF THE INVENTION According to this invention, the cyclic aminophenol compound which can be used suitably as a raw material of the thermosetting resin which has the outstanding heat resistance can be provided. Moreover, the cyclic | annular thermosetting resin which shows the outstanding heat resistance can be provided. Furthermore, by using the thermosetting resin, it is possible to achieve an excellent heat resistance, water absorption, mechanical properties, and provide an insulating film having good electrical properties.

  The present invention is a cyclic aminophenol compound having an aromatic group having a group containing an aminophenol structure in the main chain, and examples of the group containing the aminophenol structure include an (o-aminohydroxy) phenoxy group structure, As what has this structure, what has a structure represented by General formula (1) is mentioned. These can be used suitably as a thermosetting resin raw material. More specifically, for example, the cyclic aminophenol compound can be converted to a benzoxazole ring by heating by reacting with an aromatic carboxylic acid or an aromatic carboxylic acid chloride or an aromatic carboxylic acid ester under appropriate conditions. Since a resin having a hydroxyamide structure can be obtained, the aminophenol compound can be suitably used as a thermosetting resin raw material.

Further, the present invention is a thermosetting resin having an aromatic group having a substituent containing an amide phenol structure having an organic group on carbon of an amide bond in the main chain, and the substituent containing the amide phenol structure is , O-amidohydroxyphenoxy group, and those having this structure include those having the structure represented by the general formula (4). More specifically, those having a group containing an acetylene group as R in the general formula (4), or those having a structure represented by the general formula (5) or the general formula (6) are exemplified. Further, by heating these thermosetting resins, a benzoxazole ring is formed by thermal ring closure of the hydroxyamide structure. Furthermore, a resin having excellent heat resistance can be provided by making the resin structure three-dimensional by a thermal crosslinking reaction of acetylene groups. More specifically, the structure represented by the general formula (5) has higher heat resistance than the structure represented by the general formula (4) because the group adjacent to the amide group is a phenylene group. It is preferable because it is possible. Moreover, what has an ethynyl group like the structure represented by General formula (6) raises the crosslinking reaction by hardening, Therefore The heat resistance and mechanical characteristics of a cured film can be improved further, and it is preferable.
The resin film mainly composed of this polybenzoxazole resin has a hollow structure due to the cyclic structure in the resin structure, so that the resin film obtained thereby achieves a low dielectric constant and achieves both heat resistance and electrical characteristics. An insulating film can be obtained.

  In the present invention, the aromatic group represented by Ar in the general formula (1), the general formula (4), the general formula (5), and the general formula (6) includes a phenylene group, a naphthalenediyl group, and a binaphthyldiyl group. , Anthracene diyl group, phenanthrene diyl group, biphenyl diyl group, biphenylene diyl group, fluorenediyl group, biphenyl fluorenediyl group and pyridinediyl group, among which phenylene group and fluorenediyl group are Although preferable, it is not limited to these. The hydrogen atom in these groups may be substituted with an aliphatic group, an aromatic group and a fluorine atom. Examples of the aliphatic group include alkyl groups having 1 to 20 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group: carbons such as a methoxy group, an ethoxy group, a propyloxy group, and a butoxy group. Alkoxy group having 1 or more and 20 or less: Alkenyl group having 1 or more and 20 or less carbon atoms such as vinyl group, propenyl group and butenyl group: Carbon number such as ethynyl group, propynyl group and butynyl group is 1 or more 20 or less alkynyl groups: cyclopentyl group, cyclohexyl group, adamantyl group, diamantyl group and biadamantyl group and the like, and the like. Examples of the aromatic group include a phenyl group, Examples thereof include, but are not limited to, naphthyl group, phenoxy group, and naphthoxy group. Moreover, the hydrogen atom in the said aliphatic group and aromatic group may be substituted by the fluorine atom.

In the present invention, the groups represented by X ₁ and X ₂ in the general formula (1), the general formula (4), the general formula (5), and the general formula (6) include a hydrogen atom, an aliphatic group, and an aromatic group. A group composed of at least one group selected from an aromatic group, a sulfonyl group and an oxygen atom, and the aliphatic group has 1 carbon atom such as a methyl group, an ethyl group, a propyl group and a butyl group. As described above, alkynyl having 1 or more and 20 or less carbon atoms such as alkenyl group, ethynyl group, propynyl group or butynyl group having 1 or more and 20 or less carbon atoms such as alkyl group, vinyl group, propenyl group and butenyl group having 20 or less. Examples of the aromatic group include, but are not limited to, a phenyl group, a naphthalene group, a biphenyl group, and a fluorene group. Of the aliphatic group and aromatic group, a group represented by the formula (2) is preferable. The hydrogen atom in these groups may be substituted with an aliphatic group, an aromatic group and a fluorine atom. Examples of the aliphatic group include alkyl groups having 1 to 20 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group: carbons such as a methoxy group, an ethoxy group, a propyloxy group, and a butoxy group. Alkoxy group having 1 or more and 20 or less: Alkenyl group having 1 or more and 20 or less carbon atoms such as vinyl group, propenyl group and butenyl group: Carbon number such as ethynyl group, propynyl group and butynyl group is 1 or more 20 or less alkynyl groups: cycloaliphatic aliphatic groups such as cyclopentyl group and cyclohexyl group, etc., and examples of the aromatic group include phenyl group, naphthyl group, phenoxy group and naphthoxy group: However, it is not limited to these. Moreover, the hydrogen atom in the said aliphatic group and aromatic group may be substituted by the fluorine atom.

As the compound represented by the general formula (1), for example,
4,6,10,12,16,18,22,24-octakis (4-amino-3-hydroxyphenoxy) calix resorcarene, 2,8,14,20-tetramethyl-4,6,10,12 , 16,18,22,24-octakis (4-amino-3-hydroxyphenoxy) calix resorcarene, 2,8,14,20-tetraethene-4,6,10,12,16,18,22,24 -Octakis (4-amino-3-hydroxyphenoxy) calix resorcarene, 2,8,14,20-tetraethine-4,6,10,12,16,18,22,24-octakis (4-amino-3) -Hydroxyphenoxy) calix resorcarene, 2,8,14,20-tetraethynyl-4,6,10,12,16,18,22,24-octakis ( -Amino-3-hydroxyphenoxy) calix resorcalene, 2,8,14,20-tetraphenyl-4,6,10,12,16,18,22,24-octakis (4-amino-3-hydroxyphenoxy) ) Calix resorcalene, 2,8,14,20-tetra (phenylmethylene) -4,6,10,12,16,18,22,24-octakis (4-amino-3-hydroxyphenoxy) calix resor Karen, 2,8,14,20-tetra (2-phenylethylene) -4,6,10,12,16,18,22,24-octakis (4-amino-3-hydroxyphenoxy) calix resorcalen, 2,8,14,20-tetranaphthyl-4,6,10,12,16,18,22,24-octakis (4-amino-3-hydro Ciphenoxy) calix resorcalene, 2,8,14,20-tetra (naphthylmethylene) -4,6,10,12,16,18,22,24-octakis (4-amino-3-hydroxyphenoxy) calix Resorcarene, 2,8,14,20-tetra (2-naphthylethylene) -4,6,10,12,16,18,22,24-octakis (4-amino-3-hydroxyphenoxy) calix resor Karen, 2,8,14,20-tetrabiphenyl-4,6,10,12,16,18,22,24-octakis (4-amino-3-hydroxyphenoxy) calix resorcalen, 2,8,14 , 20-tetra (biphenylmethylene) -4,6,10,12,16,18,22,24-octakis (4-amino-3-hydroxyphene) Noxy) calix resorcalen, 2,8,14,20-tetra (4- (phenylmethylene) phenyl) -4,6,10,12,16,18,22,24-octakis (4-amino-3- Hydroxyphenoxy) calix resorcalen,
2,8,14,20-tetra (4- (phenylmethylene) phenylenemethylene) -4,6,10,12,16,18,22,24-octakis (4-amino-3-hydroxyphenoxy) calix resole Karen, 2,8,14,20-tetra (4- (9-phenylfluorene) phenylenemethylene) -4,6,10,12,16,18,22,24-octakis (4-amino-3-hydroxyphenoxy) ) Calix resorcarene, 2,2 ′, 8,8 ′, 14,14 ′, 20,20′-octamethyl-4,6,10,12,16,18,22,24-octakis (4-amino-) 3-hydroxyphenoxy) calix resorcarene, 2,2 ′, 8,8 ′, 14,14 ′, 20,20′-octaphenyl-4,6,10,12,16,18,22,24 Octakis (4-amino-3-hydroxyphenoxy) calix resorcarene, 2,8,14,20-tetramethyl-2,8,14,20-tetraphenyl-4,6,10,12,16,18, 22,24-octakis (4-amino-3-hydroxyphenoxy) calix resorcarene, 2,2 ′, 8,8 ′, 14,14 ′, 20,20′-octaphenyl-4,6,10,12 , 16,18,22,24-octakis (4-amino-3-hydroxyphenoxy) calix resorcalen and other compounds having a calix resorcalen structure: 25,26,27,28-tetrakis (4-amino- 3-hydroxyphenoxy) calix [4] arene, 5,11,17,23-tetrakis (1,1-dimethylethyl) -25,26,27, 8-tetrakis (4-amino-3-hydroxyphenoxy) calix [4] arene, 5,11,17,23-tetraformyl-25,26,27,28-tetrakis (4-amino-3-hydroxyphenoxy) calix [4] arene, 31,32,33,34,35-penta (4-amino-3-hydroxyphenoxy) calix [5] arene, 5,11,17,23,29-penta (1,1-dimethylethyl) ) -31,32,33,34,35-penta (4-amino-3-hydroxyphenoxy) calix [5] arene, 5,11,17,23,29-pentaformyl-31,32,33,34, 35-penta (4-amino-3-hydroxyphenoxy) calix [5] arene, 37, 38, 39, 40, 41, 42- Hexa (4-amino-3-hydroxyphenoxy) calix [6] arene, 5,11,17,23,29,35-hexa (1,1-dimethylethyl) -37,38,39,40,41,42 Hexa (4-amino-3-hydroxyphenoxy) calix [6] arene, 5,11,17,23,29,35-hexaformyl-37,38,39,40,41,42-hexa (4-amino -3-hydroxyphenoxy) calix [6] arene, 43,44,45,46,47,48,49-hepta (4-amino-3-hydroxyphenoxy) calix [7] arene, 5,11,17,23 29,35,41-hepta (1,1-dimethylethyl) -43,44,45,46,47,48,49-hepta (4-amino-3-hydro Ciphenoxy) calix [7] arene, 5,11,17,23,29,35,41-heptaformyl-43,44,45,46,47,48,49-hepta (4-amino-3-hydroxyphenoxy) Calix [7] arene, 49,50,51,52,53,54,55,56-octa (4-amino-3-hydroxyphenoxy) calix [8] arene, 5,11,17,23,29,35 , 41,47-octa (1,1-dimethylethyl) -49,50,51,52,53,54,55,56-octa (4-amino-3-hydroxyphenoxy) calix [8] arene, 5, 11, 17, 23, 29, 35, 41, 47-octaformyl-49, 50, 51, 52, 53, 54, 55, 56-octa (4-amino-3- Mud carboxymethyl phenoxy) calix [8] a compound having a calixarene structure such as arene:, and the like. Among these, 2,8,14,20-tetramethyl- which is excellent in solubility in polar solvents such as N, N-dimethylformamide and N-methylpyrrolidone which are reaction solvents used in the synthesis of the general formula (4). 4,6,10,12,16,18,22,24-octakis (4-amino-3-hydroxyphenoxy) calix resorcarene, 2,2 ', 8,8', 14,14 ', 20,20 Methyl calix resorcalene derivatives such as' -octamethyl-4,6,10,12,16,18,22,24-octakis (4-amino-3-hydroxyphenoxy) calix resorcarene, 2,8,14, 20-tetraphenyl-4,6,10,12,16,18,22,24-octakis (4-amino-3-hydroxyphenoxy) calix resorcarene, 2,2 ', 8,8', 14,14 ', 20,20'-octaphenyl-4,6,10,12,16,18,22,24-octakis (4-amino-3-hydroxyphenoxy) calix resor Phenylcalix resorcalene derivatives such as Karen, 5,11,17,23-tetrakis (1,1-dimethylethyl) -25,26,27,28-tetrakis (4-amino-3-hydroxyphenoxy) calix [4 T-butylcalix [4] arene derivatives such as arene, 5,11,17,23,29,35-hexa (1,1-dimethylethyl) -37,38,39,40,41,42-hexa ( T-Butylcalix [6] arene derivatives such as 4-amino-3-hydroxyphenoxy) calix [6] arene are preferred, but are not limited thereto. Is not something

  In the present invention, examples of the organic group represented by R in the general formula (4) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, Decyl group, adamantyl group, diamantyl group, triamantyl group, phenyl group, naphthyl group, fluorenyl group, pyridyl group, quinolyl group, quinoxalyl group, benzotriazole group, methoxy group, ethoxy group, propyloxy group, butoxy group, pentoxy group, Hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, adamantyloxy, phenoxy, naphthoxy, fluorenyloxy, pyridyloxy, quinolyloxy, quinoxalyloxy and benzotriazoleoxy Group, etc. That, without being limited thereto. The hydrogen atom in these groups may be substituted with an aliphatic group, an aromatic group and a fluorine atom. Examples of the aliphatic group include alkyl groups having 1 to 20 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group: carbons such as a methoxy group, an ethoxy group, a propyloxy group, and a butoxy group. Alkoxy group having 1 or more and 20 or less: Alkenyl group having 1 or more and 20 or less carbon atoms such as vinyl group, propenyl group and butenyl group: Carbon number such as ethynyl group, propynyl group and butynyl group is 1 or more 20 or less alkynyl groups: cyclopentyl group, cyclohexyl group, adamantyl group, diamantyl group and biadamantyl group and the like, and the like. Examples of the aromatic group include a phenyl group, Examples thereof include, but are not limited to, naphthyl group, phenoxy group, and naphthoxy group. Moreover, the hydrogen atom in the said aliphatic group and aromatic group may be substituted by the fluorine atom.

  In the present invention, the organic group represented by R in the general formula (4) may be an organic group containing an acetylene group. In this case, examples of R include ethynyl group, propynyl group, and butynyl group. , Pentynyl group, hexynyl group, heptynyl group, octynyl group, ethynyloxy group, propynyloxy group, butynyloxy group, pentynyloxy group, hexynyloxy group, heptynyloxy group, octynyloxy group, propargyl ether group, ethynylnaphthyl group, phenylethynylnaphthyl group Naphthylethynylnaphthyl, adamantylethynylnaphthyl, fluorenylethynylnaphthyl, anthrylethynylnaphthyl, ethynyladamantyl, phenylethynyladamantyl, naphthylethynyladamantyl, adamantylethynyladama Til, fluorenylethynyladamantyl, anthrylethynyladamantyl, ethynylfluorenyl, phenylethynylfluorenyl, naphthylethynylfluorenyl, adamantylethynylfluorenyl, fluorenylethynylfluorenyl Group, anthrylethynylfluorenyl group, ethynylanthryl group, phenylethynylanthryl group, naphthylethynylanthryl group, adamantylethynylanthryl group, fluorenylethynylanthryl group, anthrylethynylanthryl group, ethynylphenoxy Group, phenylethynylphenoxy group, naphthylethynylphenoxy group, adamantylethynylphenoxy group, fluorenylethynylphenoxy group, anthrylethynylphenoxy group, ethynylnaphthoxy group, phenyl Ethynylnaphthoxy group, naphthylethynylnaphthoxy group, adamantylethynylnaphthoxy group, fluorenylethynylnaphthoxy group, anthrylethynylnaphthoxy group, ethynylfluorenyloxy group, phenylethynylfluorenyloxy group, naphthylethynylfluorine Olenyloxy, adamantylethynylfluorenyloxy, fluorenylethynylfluorenyloxy, anthrylethynylfluorenyloxy, ethynylanthryloxy, phenylethynylanthryloxy, naphthylethynylanthryloxy Group, adamantylethynylanthryloxy group, fluorenylethynylanthryloxy group, anthrylethynylanthryloxy group, ethynyladamantyloxy group, adamantylethynyladamantyloxy group Containing ethynyl groups such as thio group, naphthylethynyladamantyloxy group, adamantylethynyladamantyloxy group, fluorenylethynyladamantyloxy group and anthrylethynyladamantyloxy group: ethynylphenoxyphenyl group, phenylethynylphenoxyphenyl group, naphthyl Those having an ethynylphenoxyphenyl group such as ethynylphenoxyphenyl group, adamantylethynylphenoxyphenyl group, fluorenylethynylphenoxyphenyl group and anthrylethynylphenoxyphenyl group: ethynylphenyl group, phenylethynylphenyl group, naphthylethynylphenyl group, Ethini such as adamantylethynylphenyl, fluorenylethynylphenyl and anthrylethynylphenyl Those having a phenyl group:, and the like can be mentioned, but not limited thereto. The hydrogen atom in these groups may be substituted with an aliphatic group, an aromatic group and a fluorine atom. Examples of the aliphatic group include alkyl groups having 1 to 20 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group: carbons such as a methoxy group, an ethoxy group, a propyloxy group, and a butoxy group. Alkoxy group having 1 or more and 20 or less: Alkenyl group having 1 or more and 20 or less carbon atoms such as vinyl group, propenyl group and butenyl group: Carbon number such as ethynyl group, propynyl group and butynyl group is 1 or more 20 or less alkynyl groups: cyclopentyl group, cyclohexyl group, adamantyl group, diamantyl group and biadamantyl group and the like, and the like. Examples of the aromatic group include a phenyl group, Examples thereof include, but are not limited to, naphthyl group, phenoxy group, and naphthoxy group. Moreover, the hydrogen atom in the said aliphatic group and aromatic group may be substituted by the fluorine atom.

In the present invention, as the compound represented by the general formula (4), for example, R in the general formula (4) is an example of a phenyl group in the organic group.
4,6,10,12,16,18,22,24-octakis (4-benzoylamino-3-hydroxyphenoxy) calix resorcalene, 2,8,14,20-tetramethyl-4,6,10, 12,16,18,22,24-octakis (4-benzoylamino-3-hydroxyphenoxy) calix resorcarene, 2,8,14,20-tetraethene-4,6,10,12,16,18,22 , 24-octakis (4-benzoylamino-3-hydroxyphenoxy) calix resorcalen, 2,8,14,20-tetraethine-4,6,10,12,16,18,22,24-octakis (4- Benzoylamino-3-hydroxyphenoxy) calix resorcalene, 2,8,14,20-tetraethynyl-4,6,10,1 , 16,18,22,24-octakis (4-benzoylamino-3-hydroxyphenoxy) calix resorcarene, 2,8,14,20-tetraphenyl-4,6,10,12,16,18,22 , 24-octakis (4-benzoylamino-3-hydroxyphenoxy) calix resorcarene, 2,8,14,20-tetra (phenylmethylene) -4,6,10,12,16,18,22,24- Octakis (4-benzoylamino-3-hydroxyphenoxy) calix resorcarene, 2,8,14,20-tetra (2-phenylethylene) -4,6,10,12,16,18,22,24-octakis (4-Benzoylamino-3-hydroxyphenoxy) calix resorcalene, 2,8,14,20-tetranaphthyl 4,6,10,12,16,18,22,24-octakis (4-benzoylamino-3-hydroxyphenoxy) calix resorcalene, 2,8,14,20-tetra (naphthylmethylene) -4,6 , 10,12,16,18,22,24-octakis (4-benzoylamino-3-hydroxyphenoxy) calix resorcalene, 2,8,14,20-tetra (2-naphthylethylene) -4,6 10,12,16,18,22,24-octakis (4-benzoylamino-3-hydroxyphenoxy) calix resorcarene, 2,8,14,20-tetrabiphenyl-4,6,10,12,16, 18,22,24-octakis (4-benzoylamino-3-hydroxyphenoxy) calix resorcarene, 2,8,14,2 0-tetra (biphenylmethylene) -4,6,10,12,16,18,22,24-octakis (4-benzoylamino-3-hydroxyphenoxy) calix resorcalen, 2,8,14,20-tetra (4- (Phenylmethylene) phenyl) -4,6,10,12,16,18,22,24-octakis (4-benzoylamino-3-hydroxyphenoxy) calix resorcalen, 2,8,14,20 -Tetra (4- (phenylmethylene) phenylenemethylene) -4,6,10,12,16,18,22,24-octakis (4-benzoylamino-3-hydroxyphenoxy) calix resorcarene, 2,8, 14,20-tetra (4- (9-phenylfluorene) phenylenemethylene) -4,6,10,12,16,18 22,24-octakis (4-benzoylamino-3-hydroxyphenoxy) calix resorcarene, 2,2 ′, 8,8 ′, 14,14 ′, 20,20′-octamethyl-4,6,10,12 , 16,18,22,24-octakis (4-benzoylamino-3-hydroxyphenoxy) calix resorcarene, 2,2 ′, 8,8 ′, 14,14 ′, 20,20′-octaphenyl-4 , 6,10,12,16,18,22,24-octakis (4-benzoylamino-3-hydroxyphenoxy) calix resorcarene, 2,8,14,20-tetramethyl-2,8,14,20 -Tetraphenyl-4,6,10,12,16,18,22,24-octakis (4-benzoylamino-3-hydroxyphenoxy) calix resorcalen Compounds having any calixresorcarene structure: 25,26,27,28-tetrakis (4-benzoylamino-3-hydroxyphenoxy) calix [4] arene, 5,11,17,23-tetrakis (1,1 -Dimethylethyl) -25,26,27,28-tetrakis (4-benzoylamino-3-hydroxyphenoxy) calix [4] arene, 5,11,17,23-tetraformyl-25,26,27,28- Tetrakis (4-benzoylamino-3-hydroxyphenoxy) calix [4] arene, 31,32,33,34,35-penta (4-benzoylamino-3-hydroxyphenoxy) calix [5] arene, 5,11, 17,23,29-penta (1,1-dimethylethyl) -31,32,33 34,35-penta (4-benzoylamino-3-hydroxyphenoxy) calix [5] arene, 5,11,17,23,29-pentaformyl-31,32,33,34,35-penta (4-benzoyl) Amino-3-hydroxyphenoxy) calix [5] arene,
37,38,39,40,41,42-hexa (4-benzoylamino-3-hydroxyphenoxy) calix [6] arene, 5,11,17,23,29,35-hexa (1,1-dimethylethyl) ) -37,38,39,40,41,42-hexa (4-benzoylamino-3-hydroxyphenoxy) calix [6] arene, 5,11,17,23,29,35-hexaformyl-37,38 , 39,40,41,42-hexa (4-benzoylamino-3-hydroxyphenoxy) calix [6] arene, 43,44,45,46,47,48,49-hepta (4-benzoylamino-3- Hydroxyphenoxy) calix [7] arene, 5,11,17,23,29,35,41-hepta (1,1-dimethylethyl -43,44,45,46,47,48,49-hepta (4-benzoylamino-3-hydroxyphenoxy) calix [7] arene, 5,11,17,23,29,35,41-heptaformyl-43 , 44, 45, 46, 47, 48, 49-hepta (4-benzoylamino-3-hydroxyphenoxy) calix [7] arene, 49, 50, 51, 52, 53, 54, 55, 56-octa (4 -Benzoylamino-3-hydroxyphenoxy) calix [8] arene, 5,11,17,23,29,35,41,47-octa (1,1-dimethylethyl) -49,50,51,52,53 , 54,55,56-octa (4-benzoylamino-3-hydroxyphenoxy) calix [8] arene, 5,11,17,2 , 29,35,41,47-octaformyl-49,50,51,52,53,54,55,56-octa (4-benzoylamino-3-hydroxyphenoxy) calix [8] arene and other calixarene structures Examples of the compound in which R in the general formula (4) is a methyl group include those in which the benzoylamino group is an acetylamino group in the previous compound, that is, 4, 6, 10, 12 , 16,18,22,24-octakis (4-acetylamino-3-hydroxyphenoxy) calix resorcarene, 2,8,14,20-tetramethyl-4,6,10,12,16,18,22 , 24-octakis (4-acetylamino-3-hydroxyphenoxy) calix resorcalen, 25,26,27,28-teto Lakis (4-acetylamino-3-hydroxyphenoxy) calix [4] arene, 5,11,17,23-tetrakis (1,1-dimethylethyl) -25,26,27,28-tetrakis (4-acetylamino) -3-hydroxyphenoxy) calix [4] arene, 37,38,39,40,41,42-hexa (4-acetylamino-3-hydroxyphenoxy) calix [6] arene, 5,11,17,23, 29,35-hexa (1,1-dimethylethyl) -37,38,39,40,41,42-hexa (4-acetylamino-3-hydroxyphenoxy) calix [6] arene: As an example where R in the general formula (4) is a phenylethynylnaphthyl group, Enylethynylnaphthylcarbonylamino group, ie, 4,6,10,12,16,18,22,24-octakis (4-phenylethynylnaphthylcarbonylamino-3-hydroxyphenoxy) calix resorcalene, 2, 8,14,20-tetramethyl-4,6,10,12,16,18,22,24-octakis (4-phenylethynylnaphthylcarbonylamino-3-hydroxyphenoxy) calix resorcalene, 25,26,27 , 28-tetrakis (4-phenylethynylnaphthylcarbonylamino-3-hydroxyphenoxy) calix [4] arene, 5,11,17,23-tetrakis (1,1-dimethylethyl) -25,26,27,28- Tetrakis (4-phenylethynylnaphthylcarbo Ruamino-3-hydroxyphenoxy) calix [4] arene, 37,38,39,40,41,42-hexa (4-phenylethynylnaphthylcarbonylamino-3-hydroxyphenoxy) calix [6] arene, 5,11, 17,23,29,35-hexa (1,1-dimethylethyl) -37,38,39,40,41,42-hexa (4-phenylethynylnaphthylcarbonylamino-3-hydroxyphenoxy) calix [6] arene However, it is not limited to these.

  In the present invention, examples of the organic group containing an acetylene group represented by Y in the general formula (5) include an ethynyl group, a propynyl group, a butynyl group, a pentynyl group, a hexynyl group, a heptynyl group, an octynyl group, and an ethynyloxy group. Group, propynyloxy group, butynyloxy group, pentynyloxy group, hexynyloxy group, heptynyloxy group, octynyloxy group, propargyl ether group, ethynylphenyl group, phenylethynylphenyl group, naphthylethynylphenyl group, adamantylethynylphenyl group, fluorenylethynyl Phenyl group, anthrylethynylphenyl group, ethynylnaphthyl group, phenylethynylnaphthyl group, naphthylethynylnaphthyl group, adamantylethynylnaphthyl group, fluorenylethynylnaphthyl group, anthrylethini Naphthyl group, ethynyladamantyl group, phenylethynyladamantyl group, naphthylethynyladamantyl group, adamantylethynyladamantyl group, fluorenylethynyladamantyl group, anthrylethynyladamantyl group, ethynylfluorenyl group, phenylethynylfluorenyl group, naphthylethynyl Fluorenyl group, adamantylethynylfluorenyl group, fluorenylethynylfluorenyl group, anthrylethynylfluorenyl group, ethynylanthryl group, phenylethynylanthryl group, naphthylethynylanthryl group, adamantylethynylanthryl group Group, fluorenylethynylanthryl group, anthrylethynylanthryl group, ethynylphenoxy group, phenylethynylphenoxy group, naphthylethynylphenoxy group, Damantylethynylphenoxy group, fluorenylethynylphenoxy group, anthrylethynylphenoxy group, ethynylnaphthoxy group, phenylethynylnaphthoxy group, naphthylethynylnaphthoxy group, adamantylethynylnaphthoxy group, fluorenylethynylnaphthoxy group, Anthrylethynylnaphthoxy group, ethynylfluorenyloxy group, phenylethynylfluorenyloxy group, naphthylethynylfluorenyloxy group, adamantylethynylfluorenyloxy group, fluorenylethynylfluorenyloxy group, anthryl Ethynylfluorenyloxy group, ethynylanthryloxy group, phenylethynylanthryloxy group, naphthylethynylanthryloxy group, adamantylethynylanthryloxy group, fluorenylethyl Nylanthryloxy, anthrylethynylanthryloxy, ethynyladamantyloxy, adamantylethynyladamantyloxy, naphthylethynyladamantyloxy, adamantylethynyladamantyloxy, fluorenylethynyladamantyloxy and anthrylethynyladamantyloxy Examples thereof include, but are not limited to, groups. The hydrogen atom in these groups may be substituted with an aliphatic group, an aromatic group and a fluorine atom. Examples of the aliphatic group include alkyl groups having 1 to 20 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group: carbons such as a methoxy group, an ethoxy group, a propyloxy group, and a butoxy group. Alkoxy group having 1 or more and 20 or less: Alkenyl group having 1 or more and 20 or less carbon atoms such as vinyl group, propenyl group and butenyl group: Carbon number such as ethynyl group, propynyl group and butynyl group is 1 or more 20 or less alkynyl groups: cyclopentyl group, cyclohexyl group, adamantyl group, diamantyl group and biadamantyl group and the like, and the like. Examples of the aromatic group include a phenyl group, Examples thereof include, but are not limited to, naphthyl group, phenoxy group, and naphthoxy group. Moreover, the hydrogen atom in the said aliphatic group and aromatic group may be substituted by the fluorine atom.

  In the present invention, examples of the compound having the structure represented by the general formula (5) include 4, 6, 6, as examples of ethynylphenoxy groups among the organic groups in which Y in the general formula (5) has the acetylene group. 10,12,16,18,22,24-octakis (4- (4-ethynylphenoxybenzoyl) amino-3-hydroxyphenoxy) calix resorcalene, 2,8,14,20-tetramethyl-4,6 10,12,16,18,22,24-octakis (4- (4-ethynylphenoxybenzoyl) amino-3-hydroxyphenoxy) calix resorcalene, 2,8,14,20-tetraethene-4,6,10 , 12, 16, 18, 22, 24-octakis (4- (4-ethynylphenoxybenzoyl) amino-3-hydroxyphenoxy) potassium Xxresorcarene, 2,8,14,20-tetraethine-4,6,10,12,16,18,22,24-octakis (4- (4-ethynylphenoxybenzoyl) amino-3-hydroxyphenoxy) calix resorcalen 2,8,14,20-tetraethynyl-4,6,10,12,16,18,22,24-octakis (4- (4-ethynylphenoxybenzoyl) amino-3-hydroxyphenoxy) calix resorcalen 2,8,14,20-tetraphenyl-4,6,10,12,16,18,22,24-octakis (4- (4-ethynylphenoxybenzoyl) amino-3-hydroxyphenoxy) calix resorcalen 2,8,14,20-tetra (phenylmethylene) -4,6,10,12,16,18 22,24-octakis (4- (4-ethynylphenoxybenzoyl) amino-3-hydroxyphenoxy) calix resorcarene, 2,8,14,20-tetra (2-phenylethylene) -4,6,10,12 , 16,18,22,24-octakis (4- (4-ethynylphenoxybenzoyl) amino-3-hydroxyphenoxy) calix resorcalene, 2,8,14,20-tetranaphthyl-4,6,10,12 , 16,18,22,24-octakis (4- (4-ethynylphenoxybenzoyl) amino-3-hydroxyphenoxy) calix resorcarene, 2,8,14,20-tetra (naphthylmethylene) -4,6 10,12,16,18,22,24-octakis (4- (4-ethynylphenoxybenzoyl) amino No-3-hydroxyphenoxy) calix resorcarene, 2,8,14,20-tetra (2-naphthylethylene) -4,6,10,12,16,18,22,24-octakis (4- (4 -Ethynylphenoxybenzoyl) amino-3-hydroxyphenoxy) calix resorcalen, 2,8,14,20-tetrabiphenyl-4,6,10,12,16,18,22,24-octakis (4- (4 -Ethynylphenoxybenzoyl) amino-3-hydroxyphenoxy) calix resorcalen, 2,8,14,20-tetra (biphenylmethylene) -4,6,10,12,16,18,22,24-octakis (4 -(4-Ethynylphenoxybenzoyl) amino-3-hydroxyphenoxy) calix resorcalen, 2,8,1 , 20-tetra (4- (phenylmethylene) phenyl) -4,6,10,12,16,18,22,24-octakis (4- (4-ethynylphenoxybenzoyl) amino-3-hydroxyphenoxy) calixtre Zolcarene, 2,8,14,20-tetra (4- (phenylmethylene) phenylenemethylene) -4,6,10,12,16,18,22,24-octakis (4- (4-ethynylphenoxybenzoyl) Amino-3-hydroxyphenoxy) calix resorcalene, 2,8,14,20-tetra (4- (9-phenylfluorene) phenylenemethylene) -4,6,10,12,16,18,22,24- Octakis (4- (4-ethynylphenoxybenzoyl) amino-3-hydroxyphenoxy) calix resorcare 2,2 ′, 8,8 ′, 14,14 ′, 20,20′-octamethyl-4,6,10,12,16,18,22,24-octakis (4- (4-ethynylphenoxybenzoyl) Amino-3-hydroxyphenoxy) calix resorcarene, 2,2 ′, 8,8 ′, 14,14 ′, 20,20′-octaphenyl-4,6,10,12,16,18,22,24 -Octakis (4- (4-ethynylphenoxybenzoyl) amino-3-hydroxyphenoxy) calix resorcarene, 2,8,14,20-tetramethyl-2,8,14,20-tetraphenyl-4,6 10, 12, 16, 18, 22, 24-octakis (4- (4-ethynylphenoxybenzoyl) amino-3-hydroxyphenoxy) calix resorcalen Compound having Lixresorcarene structure: 25,26,27,28-tetrakis (4- (4-ethynylphenoxybenzoyl) amino-3-hydroxyphenoxy) calix [4] arene, 5,11,17,23- Tetrakis (1,1-dimethylethyl) -25,26,27,28-tetrakis (4- (4-ethynylphenoxybenzoyl) amino-3-hydroxyphenoxy) calix [4] arene, 5,11,17,23- Tetraformyl-25,26,27,28-tetrakis (4- (4-ethynylphenoxybenzoyl) amino-3-hydroxyphenoxy) calix [4] arene, 31,32,33,34,35-penta (4- ( 4-ethynylphenoxybenzoyl) amino-3-hydroxyphenoxy) cali [5] arene, 5,11,17,23,29-penta (1,1-dimethylethyl) -31,32,33,34,35-penta (4- (4-ethynylphenoxybenzoyl) amino-3 -Hydroxyphenoxy) calix [5] arene, 5,11,17,23,29-pentaformyl-31,32,33,34,35-penta (4- (4-ethynylphenoxybenzoyl) amino-3-hydroxyphenoxy ) Calix [5] arene, 37,38,39,40,41,42-hexa (4- (4-ethynylphenoxybenzoyl) amino-3-hydroxyphenoxy) calix [6] arene, 5,11,17,23 , 29,35-hexa (1,1-dimethylethyl) -37,38,39,40,41,42-hexa (4- (4 Ethynylphenoxybenzoyl) amino-3-hydroxyphenoxy) calix [6] arene, 5,11,17,23,29,35-hexaformyl-37,38,39,40,41,42-hexa (4- (4 -Ethynylphenoxybenzoyl) amino-3-hydroxyphenoxy) calix [6] arene, 43,44,45,46,47,48,49-hepta (4- (4-ethynylphenoxybenzoyl) amino-3-hydroxyphenoxy) Calix [7] arene, 5,11,17,23,29,35,41-hepta (1,1-dimethylethyl) -43,44,45,46,47,48,49-hepta (4- (4 -Ethynylphenoxybenzoyl) amino-3-hydroxyphenoxy) calix [7] arene, 5,11 , 17, 23, 29, 35, 41-heptaformyl-43, 44, 45, 46, 47, 48, 49-hepta (4- (4-ethynylphenoxybenzoyl) amino-3-hydroxyphenoxy) calix [7] arene , 49, 50, 51, 52, 53, 54, 55, 56-octa (4- (4-ethynylphenoxybenzoyl) amino-3-hydroxyphenoxy) calix [8] arene, 5, 11, 17, 23, 29 , 35, 41, 47-octa (1,1-dimethylethyl) -49, 50, 51, 52, 53, 54, 55, 56-octa (4- (4-ethynylphenoxybenzoyl) amino-3-hydroxyphenoxy ) Calix [8] arene, 5, 11, 17, 23, 29, 35, 41, 47-octaformyl-49, 50, 5 , 52, 53, 54, 55, 56-octa (4- (4-ethynylphenoxybenzoyl) amino-3-hydroxyphenoxy) calix [8] arene and other compounds having a calix resorcalene structure: As an example where Y in the general formula (5) is a phenylethynylphenoxy group, in the above compound, (ethynylphenoxybenzoyl) amino group is a (phenylethynylphenoxybenzoyl) amino group, that is, 4, 6, 10 , 12,16,18,22,24-octakis (4- (4-phenylethynylphenoxybenzoyl) amino-3-hydroxyphenoxy) calix resorcalene, 2,8,14,20-tetramethyl-4,6 10, 12, 16, 18, 22, 24-octakis (4- (4-Fe Luethynylphenoxybenzoyl) amino-3-hydroxyphenoxy) calix resorcalen, 25,26,27,28-tetrakis (4- (4-phenylethynylphenoxybenzoyl) amino-3-hydroxyphenoxy) calix [4] arene, 5,11,17,23-tetrakis (1,1-dimethylethyl) -25,26,27,28-tetrakis (4- (4-phenylethynylphenoxybenzoyl) amino-3-hydroxyphenoxy) calix [4] arene 37,38,39,40,41,42-hexa (4- (4-phenylethynylphenoxybenzoyl) amino-3-hydroxyphenoxy) calix [6] arene, 5,11,17,23,29,35- Hexa (1,1-dimethylethyl) -37,3 8,39,40,41,42-hexa (4- (4-phenylethynylphenoxybenzoyl) amino-3-hydroxyphenoxy) calix [6] arene: can be mentioned, but is not limited thereto is not.

  In the present invention, examples of the organic group represented by Z in the general formula (6) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a phenyl group, a phenoxyphenyl group, and a naphthyl group. Examples thereof include, but are not limited to, a fluorenyl group. The hydrogen atom in these groups may be substituted with an aliphatic group, an aromatic group and a fluorine atom. Examples of the aliphatic group include alkyl groups having 1 to 20 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group: carbons such as a methoxy group, an ethoxy group, a propyloxy group, and a butoxy group. Alkoxy group having 1 or more and 20 or less: Alkenyl group having 1 or more and 20 or less carbon atoms such as vinyl group, propenyl group and butenyl group: Carbon number such as ethynyl group, propynyl group and butynyl group is 1 or more 20 or less alkynyl groups: cyclopentyl group, cyclohexyl group, adamantyl group, diamantyl group and biadamantyl group and the like, and the like. Examples of the aromatic group include a phenyl group, Examples thereof include, but are not limited to, naphthyl group, phenoxy group, and naphthoxy group. Moreover, the hydrogen atom in the said aliphatic group and aromatic group may be substituted by the fluorine atom.

  In the present invention, examples of the compound having the structure represented by the general formula (6) include 4, 6, 10, 12, 16, 18, 22, 24 as examples where Z in the general formula (6) is a hydrogen atom. -Octakis (4- (ethynylbenzoyl) amino-3-hydroxyphenoxy) calix resorcarene, 2,8,14,20-tetramethyl-4,6,10,12,16,18,22,24-octakis ( 4- (ethynylbenzoyl) amino-3-hydroxyphenoxy) calix resorcarene, 2,8,14,20-tetraethene-4,6,10,12,16,18,22,24-octakis (4- (ethynyl) Benzoyl) amino-3-hydroxyphenoxy) calix resorcarene, 2,8,14,20-tetraethine-4,6,10,12,16,18,22, 4-octakis (4- (ethynylbenzoyl) amino-3-hydroxyphenoxy) calix resorcarene, 2,8,14,20-tetraethynyl-4,6,10,12,16,18,22,24-octakis (4- (ethynylbenzoyl) amino-3-hydroxyphenoxy) calix resorcarene, 2,8,14,20-tetraphenyl-4,6,10,12,16,18,22,24-octakis (4- (Ethynylbenzoyl) amino-3-hydroxyphenoxy) calix resorcarene, 2,8,14,20-tetra (phenylmethylene) -4,6,10,12,16,18,22,24-octakis (4- (Ethynylbenzoyl) amino-3-hydroxyphenoxy) calix resorcarene, 2,8,14,20-teto (2-Phenylethylene) -4,6,10,12,16,18,22,24-octakis (4- (ethynylbenzoyl) amino-3-hydroxyphenoxy) calix resorcalen, 2,8,14,20 -Tetranaphthyl-4,6,10,12,16,18,22,24-octakis (4- (ethynylbenzoyl) amino-3-hydroxyphenoxy) calix resorcalen, 2,8,14,20-tetra ( Naphthylmethylene) -4,6,10,12,16,18,22,24-octakis (4- (ethynylbenzoyl) amino-3-hydroxyphenoxy) calix resorcalene, 2,8,14,20-tetra ( 2-naphthylethylene) -4,6,10,12,16,18,22,24-octakis (4- (ethynylbenzoyl) a Mino-3-hydroxyphenoxy) calix resorcalene, 2,8,14,20-tetrabiphenyl-4,6,10,12,16,18,22,24-octakis (4- (ethynylbenzoyl) amino-3 -Hydroxyphenoxy) calix resorcarene, 2,8,14,20-tetra (biphenylmethylene) -4,6,10,12,16,18,22,24-octakis (4- (ethynylbenzoyl) amino-3 -Hydroxyphenoxy) calix resorcarene, 2,8,14,20-tetra (4- (phenylmethylene) phenyl) -4,6,10,12,16,18,22,24-octakis (4- (ethynyl) Benzoyl) amino-3-hydroxyphenoxy) calix resorcarene, 2,8,14,20-tetra (4- (phen Rumethylene) phenylenemethylene) -4,6,10,12,16,18,22,24-octakis (4- (ethynylbenzoyl) amino-3-hydroxyphenoxy) calix resorcalene, 2,8,14,20- Tetra (4- (9-phenylfluorene) phenylenemethylene) -4,6,10,12,16,18,22,24-octakis (4- (ethynylbenzoyl) amino-3-hydroxyphenoxy) calix resorcarene, 2,2 ′, 8,8 ′, 14,14 ′, 20,20′-octamethyl-4,6,10,12,16,18,22,24-octakis (4- (ethynylbenzoyl) amino-3- Hydroxyphenoxy) calix resorcarene, 2,2 ′, 8,8 ′, 14,14 ′, 20,20′-octaphenyl-4, , 10, 12, 16, 18, 22, 24-octakis (4- (ethynylbenzoyl) amino-3-hydroxyphenoxy) calix resorcalene, 2,8,14,20-tetramethyl-2,8,14, Compounds having a calix resorcalen structure such as 20-tetraphenyl-4,6,10,12,16,18,22,24-octakis (4- (ethynylbenzoyl) amino-3-hydroxyphenoxy) calix resorcalen :, 25,26,27,28-tetrakis (4- (ethynylbenzoyl) amino-3-hydroxyphenoxy) calix [4] arene, 5,11,17,23-tetrakis (1,1-dimethylethyl) -25 , 26,27,28-tetrakis (4- (ethynylbenzoyl) amino-3-hydroxyphenoxy Ii) calix [4] arene, 5,11,17,23-tetraformyl-25,26,27,28-tetrakis (4- (ethynylbenzoyl) amino-3-hydroxyphenoxy) calix [4] arene, 31, 32,33,34,35-penta (4- (ethynylbenzoyl) amino-3-hydroxyphenoxy) calix [5] arene, 5,11,17,23,29-penta (1,1-dimethylethyl) -31 , 32,33,34,35-penta (4- (ethynylbenzoyl) amino-3-hydroxyphenoxy) calix [5] arene, 5,11,17,23,29-pentaformyl-31,32,33,34 , 35-penta (4- (ethynylbenzoyl) amino-3-hydroxyphenoxy) calix [5] arene 37,38,39,40,41,42-hexa (4- (ethynylbenzoyl) amino-3-hydroxyphenoxy) calix [6] arene, 5,11,17,23,29,35-hexa (1,1 -Dimethylethyl) -37,38,39,40,41,42-hexa (4- (ethynylbenzoyl) amino-3-hydroxyphenoxy) calix [6] arene, 5,11,17,23,29,35- Hexaformyl-37,38,39,40,41,42-hexa (4- (ethynylbenzoyl) amino-3-hydroxyphenoxy) calix [6] arene, 43,44,45,46,47,48,49- Hepta (4- (ethynylbenzoyl) amino-3-hydroxyphenoxy) calix [7] arene, 5,11,17,23 29,35,41-hepta (1,1-dimethylethyl) -43,44,45,46,47,48,49-hepta (4- (ethynylbenzoyl) amino-3-hydroxyphenoxy) calix [7] arene 5, 11, 17, 23, 29, 35, 41-heptaformyl-43, 44, 45, 46, 47, 48, 49-hepta (4- (ethynylbenzoyl) amino-3-hydroxyphenoxy) calix [7] Arene, 49, 50, 51, 52, 53, 54, 55, 56-octa (4- (ethynylbenzoyl) amino-3-hydroxyphenoxy) calix [8] arene, 5, 11, 17, 23, 29, 35 , 41, 47-octa (1,1-dimethylethyl) -49, 50, 51, 52, 53, 54, 55, 56-octa (4- (d Tinylbenzoyl) amino-3-hydroxyphenoxy) calix [8] arene, 5,11,17,23,29,35,41,47-octaformyl-49,50,51,52,53,54,55, A compound having a calix resorcalene structure such as 56-octa (4- (ethynylbenzoyl) amino-3-hydroxyphenoxy) calix [8] arene, and the like, and Z in the general formula (6) is a phenyl group As an example of the above, in the above compound, (ethynylbenzoyl) amino group is changed to (phenylethynylbenzoyl) amino group, that is, 4,6,10,12,16,18,22,24-octakis (4- ( Phenylethynylbenzoyl) amino-3-hydroxyphenoxy) calix resorcalen, 2,8,14,2 -Tetramethyl-4,6,10,12,16,18,22,24-octakis (4- (phenylethynylbenzoyl) amino-3-hydroxyphenoxy) calix resorcalen, 2,8,14,20-tetra Phenyl-4,6,10,12,16,18,22,24-octakis (4- (phenylethynylbenzoyl) amino-3-hydroxyphenoxy) calix resorcalen, 25,26,27,28-tetrakis (4 -(Phenylethynylbenzoyl) amino-3-hydroxyphenoxy) calix [4] arene, 5,11,17,23-tetrakis (1,1-dimethylethyl) -25,26,27,28-tetrakis (4- ( Phenylethynylbenzoyl) amino-3-hydroxyphenoxy) calix [4] array 37,38,39,40,41,42-hexa (4- (phenylethynylbenzoyl) amino-3-hydroxyphenoxy) calix [6] arene, 5,11,17,23,29,35-hexa (1 , 1-dimethylethyl) -37,38,39,40,41,42-hexa (4- (phenylethynylbenzoyl) amino-3-hydroxyphenoxy) calix [6] arene: It is not limited to these.

  The cyclic aminophenol compound of the present invention can be synthesized by reducing the nitro group of the reaction product by reacting the hydroxyl group of the cyclic hydroxyaromatic compound with the nitro compound and further performing a reduction reaction. It is not limited to this synthesis method.

式（１）、式（７）、式（９）中のＡｒは芳香族基を示す。式（１）、式（７）、式（９）中の式中のＸ₁およびＸ₂は、それぞれ独立して、前記脂肪族基、芳香族基、スルホニル基および水素原子の中から選ばれる少なくとも１種の基を示し、互いに同一であっても異なっていても良い。式（１）、式（７）、式（９）中のｍは、３以上、２０以下の整数を示す。式（１）、式（７）、式（９）中のｎは、１以上、３以下の整数を示す。 Among the cyclic aminophenol compounds of the present invention, the cyclic aminophenol compound represented by the general formula (1) can be synthesized, for example, by the following route.

Ar in Formula (1), Formula (7), and Formula (9) represents an aromatic group. X ₁ and X ₂ in formulas (1), (7), and (9) are each independently selected from the aliphatic groups, aromatic groups, sulfonyl groups, and hydrogen atoms. At least one kind of group is shown and may be the same or different. M in Formula (1), Formula (7), and Formula (9) represents an integer of 3 or more and 20 or less. N in Formula (1), Formula (7), and Formula (9) represents an integer of 1 or more and 3 or less.

First, as starting materials, a cyclic hydroxy aromatic compound represented by the general formula (7) and a fluoronitrophenyl benzyl ether represented by the general formula (8) are used using a base such as potassium carbonate or sodium carbonate. By carrying out an ether bond formation reaction, a cyclic nitrophenoxy compound having a hydroxyl group protected by a benzyl ether group, represented by the general formula (9), is obtained.
By treating this compound with palladium-activated carbon or platinum-activated carbon under a hydrogen atmosphere, or with tin or tin chloride under acidic conditions, a cyclic aminophenol compound represented by the general formula (1) is obtained. can get.

  In the present invention, the cyclic compound represented by the general formula (7) is a calix resorcalene compound obtained by synthesizing a hydroxy aromatic compound and an aldehyde with an acid catalyst, for example, 2,8. , 14,20-tetramethylcalix resorcalen, 2,8,14,20-tetraphenylcalix resorcalen, and the like, and synthesized by reacting an alkylhydroxy aromatic compound and formaldehyde with an acid catalyst. Calixarene compounds such as 5,11,17,23-tetrakis (1,1-dimethylethyl) calix [4] arene, 5,11,17,23,29-penta (1,1-dimethylethyl) calix [5] arene, 5, 11, 17, 23, 29, 35-hexa (1,1- Methylethyl) calix [6] arene, 5,11,17,23,29,35,41-hepta (1,1-dimethylethyl) calix [7] arene and 5,11,17,23,29,35, 41,47-octa (1,1-dimethylethyl) calix [8] arene and the like, and compounds obtained by further modifying these alkyl groups, such as calix [4] arene, calix [5] arene, Examples thereof include, but are not limited to, calix [6] arene, calix [7] arene and calix [8] arene.

The thermosetting resin of the present invention can be produced by synthesizing a cyclic aminophenol compound of the present invention and a carboxylic acid halide or a carboxylic acid ester to produce an amide bond. It is not limited to this synthesis method.
Among the cyclic thermosetting resins of the present invention, the cyclic thermosetting resin represented by the general formula (4) can be synthesized, for example, by the following route.

式（１）、式（４）中のＡｒは芳香族基を、Ｘは前記脂肪族基、芳香族基、スルホニル基および酸素原子の中から選ばれる少なくとも1種の基を示す。式（４）および式（１０）中のＲは有機基を示す。式（７）中のＱはハロゲン原子または、アルコキシ基、フェノキシ基、ピリジルオキシ基、キノリルオキシ基、キノキサリルオキシ基、ベンゾトリアゾールオキシ基の中から選ばれる基を示す。式（４）および式（１０）中のｎは１以上、３以下の整数を、ｍは、３以上、２０以下の整数を示す。

In the formulas (1) and (4), Ar represents an aromatic group, and X represents at least one group selected from the aliphatic group, aromatic group, sulfonyl group and oxygen atom. R in Formula (4) and Formula (10) represents an organic group. Q in the formula (7) represents a halogen atom or a group selected from an alkoxy group, a phenoxy group, a pyridyloxy group, a quinolyloxy group, a quinoxalyloxy group, and a benzotriazoleoxy group. N in Formula (4) and Formula (10) represents an integer of 1 or more and 3 or less, and m represents an integer of 3 or more and 20 or less.

  The compound having a structure represented by the general formula (4) of the present invention includes a compound having a structure represented by the general formula (1) and a carboxylic acid halide or carboxylic acid ester represented by the general formula (10). The compound represented by the general formula (1) is first dissolved or suspended in a suitable solvent to obtain an amide bond by condensation reaction with a compound. A compound represented by the formula (10) is added, mixed and reacted. At this time, the preparation of the compound represented by the general formula (1) and the carboxylic acid halide or carboxylic acid ester may be performed simultaneously. In addition, the compound represented by the general formula (1) and the carboxylic acid halide or carboxylic acid ester may be added in the form of a solid or may be added after being dissolved in an appropriate solvent.

  Examples of the carboxylic acid halide and the carboxylic acid ester represented by the general formula (10) include benzoic acid, naphthalenecarboxylic acid, adamantanecarboxylic acid, diamantanecarboxylic acid, ethynylbenzoic acid, propynylbenzoic acid, and phenylethynyl. Benzoic acid, bisphenylethynylbenzoic acid, naphthylethynylbenzoic acid, adamantylethynylbenzoic acid, ethynylnaphthalenecarboxylic acid, propynylnaphthalenecarboxylic acid, phenylethynylnaphthalenecarboxylic acid, bisphenylethynylnaphthalenecarboxylic acid, naphthylethynylnaphthalenecarboxylic acid and adamantylethynyl Chloride, bromide, iodide, methyl ester, phenyl ester, pyridyl ester, carboxylic acid compounds such as naphthalenecarboxylic acid, Noryl ester, quinoxalyl ester and benzotriazole ester, and the like can be mentioned, but not limited thereto. These may be used alone or in combination of two or more. The hydrogen atom in these groups may be substituted with an aliphatic group, an aromatic group and a fluorine atom. Examples of the aliphatic group include alkyl groups having 1 to 20 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group: carbons such as a methoxy group, an ethoxy group, a propyloxy group, and a butoxy group. Alkoxy group having 1 or more and 20 or less: Alkenyl group having 1 or more and 20 or less carbon atoms such as vinyl group, propenyl group and butenyl group: Carbon number such as ethynyl group, propynyl group and butynyl group is 1 or more 20 or less alkynyl groups: cyclopentyl group, cyclohexyl group, adamantyl group, diamantyl group and biadamantyl group and the like, and the like. Examples of the aromatic group include a phenyl group, Examples thereof include, but are not limited to, naphthyl group, phenoxy group, and naphthoxy group. Moreover, the hydrogen atom in the said aliphatic group and aromatic group may be substituted by the fluorine atom.

In the formation reaction of the compound having the structure represented by the general formula (4), the solvent is not particularly limited. For example, benzene, toluene, tetrahydrofuran, N-methylpyrrolidone, cyclohexanone, γ- Examples include butyrolactone, dichloromethane and chloroform and dimethyl sulfoxide.
In order to accelerate the reaction, a base such as triethylamine, N, N-dimethylformamide and pyridine may be added.
The molar ratio of the raw materials used in the reaction is such that the carboxylic acid halide or carboxylic acid ester is 1 equivalent or more and 2 equivalents or less with respect to the hydroxyl group of the compound represented by the general formula (1). Preferably, it is 1 equivalent times or more and 1.5 equivalent times or less, more preferably 1 equivalent time or more and 1.1 equivalent times or less.

The reaction temperature in the reaction is not particularly limited because it depends on the activity of the reaction of each compound. However, when a carboxylic acid halide is used, it is preferably −80 ° C. or higher and 100 ° C. or lower, preferably, It is above the freezing point and below 30 ° C. More preferably, it is -10 degreeC or more and 10 degrees C or less. When a carboxylic acid ester is used, it is preferably 0 ° C. or higher and 150 ° C. or lower, and preferably 50 ° C. or higher and 150 ° C. or lower.
Moreover, if it is more than the said upper limit, there exists a possibility that a carboxylic acid halide or carboxylic acid ester may react with the hydroxyl group of the compound represented by General formula (1).
The reaction time may be appropriately determined depending on the activity and reaction temperature of each compound, but is preferably 5 minutes or longer and 7 days or shorter, preferably 10 minutes or longer and 12 hours or shorter. .
The product obtained by reacting under the above conditions is precipitated by dropping or injecting the reaction solution into a solvent in which the product is not dissolved, such as water, hexane, methanol, etc., and filtering or centrifuging the precipitate. It can be obtained separately from the solution by a method or the like. In addition, when the compound represented by the general formula (1) is reacted with the carboxylic acid halide or the carboxylic acid ester without excess or deficiency, the reaction is performed in an appropriate solvent in which the product is dissolved, and after the reaction is completed, If there is an insoluble material such as a salt, the reaction solution in which only the target product is dissolved may be removed and used as it is for the intended purpose.

  As a method for producing a compound having a structure represented by the general formula (5) and the general formula (6) of the present invention, in the synthesis method of the cyclic thermosetting resin represented by the general formula (4), the general formula By using a benzoic acid halide or benzoic acid ester having an acetylene group as the carboxylic acid halide or carboxylic acid ester represented by (10), it can be produced in the same manner.

式（１１）、式（１２）、式（１３）中のＳは脱離基を、式（１０’）、式（１０’’）、式（１０’’’）、式（１４）、式（１５）、式（１６）中のＺは保護基または有機基を示す。また、ｐは１以上、５以下の整数を示す。 The benzoic acid halide or benzoic acid ester having an acetylene group can be synthesized, for example, as follows.

S in Formula (11), Formula (12), and Formula (13) is a leaving group, Formula (10 ′), Formula (10 ″), Formula (10 ′ ″), Formula (14), Formula (15), Z in formula (16) represents a protecting group or an organic group. P represents an integer of 1 to 5.

As an example of a method for obtaining the compound represented by the general formula (12), it can be obtained by an esterification reaction of benzoic acid in which the benzene ring is substituted with a leaving group S represented by the general formula (11). Alternatively, a benzoic acid halide is obtained by reacting a compound represented by the general formula (11) with a halogenating agent to obtain a halogenated benzoate, and further esterifying the obtained halide to obtain a benzoic acid ester. Is obtained.
When the ester reaction is an esterification reaction between a compound represented by the general formula (11) and methanol, a methyl esterified product represented by the general formula (12) is obtained. Moreover, when the said halogenation reaction is reaction of the compound represented by General formula (11), and thionyl chloride, the benzoic acid chloride represented by General formula (13) is obtained, and also it reacts with methanol. To give a methyl esterified product (general formula (12)).
Next, a methyl ester compound represented by the general formula (12) and a compound in which one side of the acetylene represented by the general formula (14) is substituted with a Z group are subjected to a coupling reaction, whereby the general formula (10 ′ A benzoic acid ester product having an acetylene group represented by In the coupling reaction, for example, a transition metal catalyst such as palladium may be used.
The leaving group S is preferably a group that can be easily removed from an aromatic ring by a coupling reaction under a catalyst, and is preferably a halogen atom such as fluorine, chlorine, bromine, or iodine, or a trifluoromethanesulfonoxy group. Can be mentioned.

Next, the compound represented by the general formula (10 ′) is demethylated from an acetyl group using a basic alkali metal hydroxide such as potassium hydroxide, sodium hydroxide or calcium hydroxide, An alkali metal salt of a benzoic acid derivative represented by the formula (15) is obtained. Here, when Z is an acetylene protecting group such as a trimethylsilyl group or a hydroxypropyl group, deprotection proceeds at the same time, and an ethynyl group can be obtained.
Moreover, the benzoic acid represented by General formula (16) can be obtained by acid-treating the alkali metal salt (general formula (15)) of the benzoic acid derivative obtained above.

  Next, by treating the alkali metal salt of the benzoic acid derivative represented by the general formula (15) or the benzoic acid represented by the general formula (16) with a halogenating agent, the general formula (10 ″) The benzoic acid halide which has an acetylene group represented by these can be obtained. Further, an esterification reaction of the obtained halide yields a benzoic acid ester (general formula (10 ′ ″)). When the halogenation reaction is a reaction between a compound represented by the general formula (15) or the general formula (16) and thionyl chloride, a benzoic acid chloride represented by the general formula (10 '') is obtained. Further, when the esterification reaction is an esterification reaction with pyridinol, a pyridyl esterified product represented by the general formula (17 ′ ″) is obtained.

  The insulating film material of the present invention can contain various additives in addition to the cyclic thermosetting resin as a film forming component, depending on the purpose. Examples of the various additives include surfactants, coupling agents represented by silanes, radical initiators that generate oxygen radicals and sulfur radicals by heating, and catalysts such as disulfides.

  The insulating film material of the present invention can be used as a coating varnish after being dissolved in a suitable organic solvent or uniformly dispersed. For example, first, the insulating film material is dissolved or uniformly dispersed in an organic solvent to form a varnish, which is applied to an appropriate support such as glass, fiber, metal, silicon wafer, ceramic substrate, etc. to form a coating film To do. Examples of the application method include dipping, screen printing, spraying, spin coating, and roll coating. Next, the coating film is dried by heating to volatilize the solvent to obtain a tack-free coating film. Then, it is preferable to heat-treat and convert into a polybenzoxazole resin crosslinked body. Moreover, it can also be used as a polybenzoxazole resin soluble in a solvent by selecting a cyclic aminophenol compound and a carboxylic acid chloride component.

As the organic solvent for dissolving or dispersing the insulating film material of the present invention, a solvent that completely dissolves the solid content is preferable. For example, N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethyl Sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1 , 3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxypropionate, methyl ethyl Ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone and tetrahydrofuran. These may use 1 type and may mix and use 2 or more types.
The amount of the solvent used in preparing the coating varnish is not particularly limited as long as it can dissolve the insulating film material completely, and the amount used is appropriately adjusted according to the application. Generally, the solvent content in the varnish is preferably about 70 to 95% by weight.

  The insulating film of the present invention is obtained by evaporating the solvent at a temperature in the range of 80 to 200 ° C., using the insulating film material as described above. By heat treatment at temperature, the amide phenol structure in the cyclic thermosetting resin undergoes a cyclization condensation reaction and a cross-linking reaction to become a resin layer mainly composed of polybenzoxazole, thereby obtaining the insulating film of the present invention. it can. Examples of the heat treatment method include a method in which the temperature is raised gradually in an oven or the like, and a method in which the heat treatment is performed at a stretch using a hot plate or the like. The atmosphere in the heat treatment is preferably performed in an inert gas atmosphere or in a vacuum. Examples of the inert gas include nitrogen gas and argon. At this time, the oxygen concentration in the system is preferably 100 ppm or less.

The thickness of the insulating film of the present invention varies depending on the purpose of use, but is usually in the range of 0.1 to 100 μm, preferably 0.1 to 50 μm, more preferably 0.1 to 20 μm.
The insulating film material and insulating film of the present invention can be used for semiconductor interlayer insulating films and protective films, multilayer circuit interlayer insulating films, flexible copper-clad cover coats, solder resist films, liquid crystal alignment films, and the like.

As an example of the case where the insulating film of the present invention is used for an interlayer insulating film for multilayer wiring of a semiconductor device, first, when improving adhesiveness, an adhesive coating agent is applied onto a semiconductor substrate, and a coating film is applied. Form. Examples of the coating method include spin coating with a spinner, spray coating with a spray coater, dipping, printing, and roll coating. Thereafter, the coating film is pre-baked at a temperature equal to or higher than the boiling point of the organic solvent, and the organic solvent in the adhesive coating agent is evaporated and dried to form an adhesive coating film.
Next, on the adhesive coating film, the solution of the insulating film material of the present invention is applied by the same method as described above to form a coating film. Next, the coating film is pre-baked under the above conditions, the organic solvent in the solution of the insulating film material is evaporated to dryness, and further, the amide phenol structure is closed to the oxazole structure by heat treatment, and interlayer insulation is achieved. A film can be formed.
Similarly, a resin film can be formed to form a surface protective film.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited at all by these examples.

For the insulating films (films) produced in the following examples and comparative examples, the dielectric constant, heat resistance, glass transition temperature, water absorption rate, and elastic modulus are measured by the following methods, and the insulating film (film) cross section is measured. Was observed.
(1) Relative permittivity Based on JIS-K6911, it measured with the frequency of 100 kHz using HP-4284A Precision LCR meter by a Hewlett-Packard company.
(2) Heat resistance Using a TG / DTA6200 manufactured by Seiko Instruments Inc., the temperature at a weight loss of 5% was measured under a flow of nitrogen gas at 200 mL / min and a temperature increase rate of 10 ° C / min.
(3) Glass transition temperature (Tg)
Using a DMS6100 manufactured by Seiko Instruments Inc., measured in tension mode under a flow of nitrogen gas of 300 mL / min under the conditions of a measurement frequency of 1 Hz and a heating rate of 3 ° C./min, the peak top temperature of loss tangent (tan δ) The glass transition temperature was taken.
(4) Water Absorption Rate The rate of weight change after a 5 cm square and 10 μm thick test film was immersed in pure water at 23 ° C. for 24 hours was calculated.
(5) Elastic modulus Using an ultrafine hardness meter ENT-1100 manufactured by Elionix, the measurement was performed at a maximum load of 10 mg and a load speed of 1 mg / sec.

Example 1
60 ml of concentrated hydrochloric acid was slowly added dropwise to a solution of 66.1 g (600 mmol) of resorcinol, 26.4 g (600 mmol) of acetaldehyde, 120 ml of ion-exchanged water, and 120 ml of ethanol. After stirring at 75 ° C. for 2 hours, the reaction solution was filtered. The filter cake was washed twice with a mixed solution of 500 ml of ion-exchanged water and 500 ml of ethanol, and dried under reduced pressure at 50 ° C. for 2 days to give 2,8,14,20-tetramethylcalix resorcalen 53. 5 g was obtained (65% yield). The resulting 2,8,14,20-tetramethylcalix resorcarene 10 g (18.4), 3-fluoro-6-nitrophenyl benzyl ether 43.6 g (176.4 mmol), N, N-dimethylformamide 160 mL To the solution, 50.0 g (361 mmol) of potassium carbonate was added. After stirring at 135 ° C. for 12 hours, the reaction solution was filtered. The filtrate was added dropwise to 300 mL of ion exchange water. The precipitated solid was washed twice with 300 mL of methanol and dried under reduced pressure at 50 ° C. for 2 days to give 2,8,14,20-tetramethyl-4,6,10,12,16,18,22 as a yellow solid. , 24-octakis (4-nitro-3-benzyloxyphenoxy) calix resorcalen (10.7 g) was obtained (49% yield).
9.9 g of 2,8,14,20-tetramethyl-4,6,10,12,16,18,22,24-octakis (4-nitro-3-benzyloxyphenoxy) calix resorcalen obtained ( 4.2 mmol) and 0.43 g (0.4 mmol) of 10% palladium activated carbon and 60 mL of N, N-dimethylformamide were stirred at room temperature for 36 hours in a hydrogen atmosphere, and then the reaction solution was filtered. The filtrate was added dropwise to 600 mL of ion exchange water. The precipitated solid was washed three times with 600 mL of ion-exchanged water and dried under reduced pressure at 50 ° C. for 2 days, whereby 2,8,14,20-tetramethyl-4,6,10,12,16,18 as a brown solid. , 22,24-octakis (4-amino-3-hydroxyphenoxy) calix resorcarene 4.0 g was obtained (yield 69.1%).
The various measured values regarding the obtained compound are shown below. These data indicate that the obtained compound is the target product.
¹ H-NMR (400 MHz, DMSO-d ₆ , ppm): δ1.4-1.6 (12H), δ4.4-5.2 (20H), δ5.8-7.3 (32H), δ8. 4-9.7 (8H)
IR (KBr, / cm): 3371, 3039, 2948, 1521, 1514, 1485
Elemental analysis: [theoretical value] C: 68.56%, H: 5.18%, N: 8.00%, O: 18.27%, [actual value] C: 67.03%, H: 5. 10%

Example 2
2,8,14,20-Tetramethyl-4,6,10,12,16,18,22,24-octakis (4-amino-3-hydroxyphenoxy) calix resorcalen obtained in Example 1. 5 g (1.1 mmol) and 6.0 mL of dehydrated N-methylpyrrolidone were dissolved in a dry nitrogen atmosphere, and then cooled to −10 ° C. To this, 1.0 g (9.0 mmol) of benzoic acid chloride was slowly added, taking care not to raise the temperature above 5 ° C. After the addition, the mixture was stirred at 20 ° C. for 2 hours. The reaction solution was added dropwise to 50 mL of ion exchange water. The precipitated solid was washed twice with 50 mL of methanol, further washed twice with 50 mL of ion-exchanged water, and dried under reduced pressure at 50 ° C. for 2 days, whereby 2,8,14,20-tetramethyl-4, 6,10,12,16,18,22,24-octakis (4-benzoylamino-3-hydroxyphenoxy) calix resorcalen 0.38 g was obtained (yield 15.9%).
The various measured values regarding the obtained compound are shown below. These data indicate that the obtained compound is the target product.
¹ H-NMR (400 MHz, DMSO-d ₆ , ppm): δ1.4-1.6 (12H), δ4.4-4.6 (4H), δ6.1-6.8 (16H) δ7.3 -8.2 (56H), δ9.5-9.6 (8H), δ9.9-10.1 (8H)
IR (KBr, / cm): 3250, 3031, 2905, 1645, 1604
Elemental analysis: [theoretical value] C: 73.11%, H: 4.69%, N: 5.02%, O: 17.19%, [actual value] C: 75.21%, H: 5. 00%

Example 3
2,8,14,20-Tetramethyl-4,6,10,12,16,18,22,24-octakis (4-benzoylamino-3-hydroxyphenoxy) calix resorcalen obtained in Example 2 0.3 g was dissolved in 2.0 g of N-methyl-2-pyrrolidone and filtered through a Teflon (R) filter having a pore size of 0.2 μm to obtain a varnish. This varnish was applied onto a silicon wafer on which aluminum was deposited using a spin coater. At this time, the rotation speed and time of the spin coater were set so that the film thickness after the heat treatment was about 0.5 μm. After coating, after drying for 240 seconds on a 90 ° C. hot plate, the film of benzoxazole compound is obtained by heating at 350 ° C. for 60 minutes using an oven in which nitrogen is introduced and the oxygen concentration is controlled to 100 ppm or less. It was. Aluminum was vapor-deposited on the film and patterned to form electrodes of a predetermined size. The silicon wafer side aluminum and the capacitance of this electrode are measured. After measurement, the electrode adjacent portion of the film is etched with oxygen plasma, and the film thickness is measured with a surface roughness meter, so that the dielectric constant at a frequency of 1 MHz is obtained. The calculated value was 2.99. The heat resistance, Tg, water absorption, and elastic modulus are also summarized in Table 1.

Example 4
To a solution of 41.7 g (378 mmol) of resorcinol, 40.1 g (378 mmol) of benzaldehyde and 230 ml of ethanol, 60 ml of concentrated hydrochloric acid was slowly added dropwise. After stirring at 75 ° C. for 42 hours, the reaction solution was filtered. The filter cake was washed twice with 500 ml of ion-exchanged water, further washed twice with 500 ml of ethanol, and dried under reduced pressure at 50 ° C. for 2 days. 72.0 g was obtained (yield 96%). The obtained 2,8,14,20-tetraphenylcalix resorcarene 14.6 g (18.4 mmol), 3-fluoro-6-nitrophenylbenzyl ether 43.6 g (176.4 mmol), N, N-dimethyl To a solution of 160 ml formamide, 50.0 g (361 mmol) potassium carbonate was added. After stirring at 135 ° C. for 12 hours, the reaction solution was filtered. The filtrate was added dropwise to 300 mL of ion exchange water. The precipitated solid was washed twice with 300 mL of methanol and dried under reduced pressure at 50 ° C. for 2 days to give 2,8,14,20-tetraphenyl-4,6,10,12,16,18,22 as a yellow solid. , 24-octakis (4-nitro-3-benzyloxyphenoxy) calix resorcalen 29.2 g (61% yield).
The obtained 2,8,14,20-tetraphenyl-4,6,10,12,16,18,22,24-octakis (4-nitro-3-benzyloxyphenoxy) calix resorcalen 20.0 g ( 7.7 mmol) and 0.65 g (0.61 mmol) of 10% palladium activated carbon and 120 mL of N, N-dimethylformamide were stirred at room temperature for 36 hours in a hydrogen atmosphere, and then the reaction solution was filtered. The filtrate was added dropwise to 1200 mL of ion exchange water. The precipitated solid was washed three times with 600 mL of ion-exchanged water and dried under reduced pressure at 50 ° C. for 2 days, whereby 2,8,14,20-tetraphenyl-4,6,10,12,16,18 as a brown solid. , 22,24-octakis (4-amino-3-hydroxyphenoxy) calix resorcarene (yield 62%) was obtained.
The various measured values regarding the obtained compound are shown below. These data indicate that the obtained compound is the target product.
¹ H-NMR (400 MHz, DMSO-d ₆ , ppm): δ 4.6-5.6 (20H), δ 5.8-7.3 (52H), δ 8.4-9.7 (8H)
IR (KBr, / cm): 3365, 3033, 2952, 1583, 1521, 1490
Elemental analysis: [theoretical value] C: 72.80%, H: 4.89%, N: 6.79%, O: 15.52%, [actual value] C: 73.30%, H: 4. 99%

Example 5
2,8,14,20-Tetraphenyl-4,6,10,12,16,18,22,24-octakis (4-amino-3-hydroxyphenoxy) calix resorcalene obtained in Example 4 0 g (0.6 mmol) and 6.0 mL of dehydrated N-methylpyrrolidone were dissolved in a dry nitrogen atmosphere and then cooled to −10 ° C. To this, 1.23 g (5.1 mmol) of 4-ethynylbenzoic acid chloride was slowly added, taking care not to raise the temperature above 5 ° C. After the addition, the mixture was stirred at 20 ° C. for 2 hours. The reaction solution was added dropwise to 50 mL of ion exchange water. The precipitated solid was washed twice with 50 mL of methanol, further twice with 50 mL of ion-exchanged water, and dried under reduced pressure at 50 ° C. for 2 days, whereby 2,8,14,20-tetraphenyl-4, There was obtained 1.27 g of 6,10,12,16,18,22,24-octakis (4- (4-phenylethynyl) benzoylamino-3-hydroxyphenoxy) calix resorcalen (yield 64.1%). .
The various measured values regarding the obtained compound are shown below. These data indicate that the obtained compound is the target product.
¹ H-NMR (400 MHz, DMSO-d ₆ , ppm): δ 5.4-5.6 (4H), δ 6.1-6.8 (36H), δ 7.3-8.2 (88H), δ 9. 5-9.6 (8H), δ9.9-10.1 (8H)
IR (KBr, / cm): 3251, 3030, 2903, 2214, 1643, 1600
Elemental analysis: [theoretical value] C: 80.47%, H: 4.42%, N: 3.41%, O: 11.69%, [actual measurement value] C: 80.98%, H: 4. 51%

Example 6
2,8,14,20-Tetraphenyl-4,6,10,12,16,18,22,24-octakis (4- (4-phenylethynyl) benzoylamino-3-hydroxy obtained in Example 5 Samples for evaluation were obtained in the same manner as in Example 3 using 0.3 g of phenoxy) calix resorcarene, and the measurement results are summarized in Table 1.

Example 7
5,11,17,23-tetrakis (1,1-dimethylethyl) -25,26,27,28-tetrakis (4-amino-3-hydroxyphenoxy) calix [4] arene (manufactured by Sugai Chemical Co., Ltd.) 50 g ( 77.4 mmol), 51.5 g (376 mmol) of potassium carbonate was added to a solution of 91.5 g (370.0 mmol) of 3-fluoro-6-nitrophenylbenzyl ether and 400 mL of N, N-dimethylformamide. After stirring at 135 ° C. for 12 hours, the reaction solution was filtered. The filtrate was added dropwise to 3000 mL of ion exchange water. The precipitated solid was washed twice with 600 mL of methanol and dried under reduced pressure at 50 ° C. for 2 days to give 5,11,17,23-tetrakis (1,1-dimethylethyl) -25,26,27 as a white yellow solid. , 28-tetrakis (4-nitro-3-benzyloxyphenoxy) calix [4] arene 76.1 g (yield 63%).
The obtained 5,11,17,23-tetrakis (1,1-dimethylethyl) -25,26,27,28-tetrakis (4-nitro-3-benzyloxyphenoxy) calix [4] arene 62.2 g ( (39.9 mmol) and 1.60 g (1.60 mmol) of 10% palladium activated carbon and 400 mL of N, N-dimethylformamide were stirred at room temperature for 36 hours in a hydrogen atmosphere, and then the reaction solution was filtered. The filtrate was added dropwise to 4000 mL of ion exchange water. The precipitated solid was washed with 600 mL of ion-exchanged water three times and dried under reduced pressure at 50 ° C. for 2 days, whereby 5,11,17,23-tetrakis (1,1-dimethylethyl) -25,26, 34.5 g of 27,28-tetrakis (4-amino-3-hydroxyphenoxy) calix [4] arene was obtained (yield 80.2%).
The various measured values regarding the obtained compound are shown below. These data indicate that the obtained compound is the target product.
¹ H-NMR (400 MHz, DMSO-d ₆ , ppm): δ0.5-1.5 (36H), δ4.5-5.2 (16H), δ5.8-7.3 (20H), δ8. 4-9.7 (4H)
IR (KBr, / cm): 3361, 3035, 2956, 1581, 1519, 1450
Elemental analysis: [theoretical value] C: 75.81%, H: 7.11%, N: 5.20%, O: 11.88%, [actual value] C: 75.00%, H: 5. 53%

Example 8
5,11,17,23-tetrakis (1,1-dimethylethyl) -25,26,27,28-tetrakis (4-amino-3-hydroxyphenoxy) calix [4] arene obtained in Example 7. 5 g (1.4 mmol) and 8.0 mL of dehydrated N-methylpyrrolidone were dissolved in a dry nitrogen atmosphere, and then cooled to −10 ° C. Here, 1.4 g (5.8 mmol) of 4-ethynylbenzoic acid chloride was slowly added while taking care not to raise the temperature to 5 ° C. or higher. After the addition, the mixture was stirred at 20 ° C. for 2 hours. The reaction solution was added dropwise to 60 mL of ion exchange water. The precipitated solid was washed twice with 50 mL of methanol, further washed twice with 50 mL of ion-exchanged water, and dried under reduced pressure at 50 ° C. for 2 days, whereby 5,11,17,23-tetrakis (1,1 -Dimethylethyl) -25,26,27,28-tetrakis (4- (4-phenylethynyl) benzoylamino-3-hydroxyphenoxy) calix [4] arene 2.3 g (yield 87.2%) .
The various measured values regarding the obtained compound are shown below. These data indicate that the obtained compound is the target product.
¹ H-NMR (400 MHz, DMSO-d ₆ , ppm): δ0.5-1.5 (36H), δ4.5-4.9 (8H), δ6.1-6.8 (4H), δ6. 9-7.2 (8H), δ 7.3-8.2 (44H), δ 9.5-9.6 (4H), δ 9.9-10.1 (4H)
IR (KBr, / cm): 3252, 3028, 2899, 2212, 1638, 1612
Elemental analysis: [theoretical value] C: 81.16%, H: 5.75%, N: 2.96%, O: 10.14%, [actual value] C: 79.96%, H: 5. 11%

Example 9
5,11,17,23-Tetrakis (1,1-dimethylethyl) -25,26,27,28-tetrakis (4- (4-phenylethynyl) benzoylamino-3-hydroxyphenoxy obtained in Example 8 ) Calix [4] arene 0.3 g was obtained in the same manner as in Example 3 to obtain evaluation samples, and the measurement results are summarized in Table 1.

Example 10
5,11,17,23,29,35-Hexa (1,1-dimethylethyl) -37,38,39,40,41,42-Hexa (4-amino-3-hydroxyphenoxy) calix [6] arene (Sugai Chemical Co., Ltd.) 50 g (51.4 mmol), 3-fluoro-6-nitrophenylbenzyl ether 91.5 g (370.0 mmol), N, N-dimethylformamide 400 mL in a solution of potassium carbonate 52.0 g (376 mmol) ) Was added. After stirring at 135 ° C. for 12 hours, the reaction solution was filtered. The filtrate was added dropwise to 3000 mL of ion exchange water. The precipitated solid was washed twice with 600 mL of methanol and dried under reduced pressure at 50 ° C. for 2 days to give 5,11,17,23,29,35-hexa (1,1-dimethylethyl) -37 as a white yellow solid. , 38, 39, 40, 41, 42-hexa (4-nitro-3-benzyloxyphenoxy) calix [6] arene (86.5 g) was obtained (yield 72%).
The resulting 5,11,17,23,29,35-hexa (1,1-dimethylethyl) -37,38,39,40,41,42-hexa (4-nitro-3-benzyloxyphenoxy) calix [6] 81.1 g (34.7 mmol) of arene, 2.10 g (2.10 mmol) of 10% palladium activated carbon and 500 mL of N, N-dimethylformamide were stirred at room temperature for 36 hours in a hydrogen atmosphere, Was filtered. The filtrate was added dropwise to 5000 mL of ion exchange water. The precipitated solid was washed with 600 mL of ion-exchanged water three times and dried under reduced pressure at 50 ° C. for 2 days, whereby 5,11,17,23,29,35-hexa (1,1-dimethylethyl)- 37,38,39,40,41,42-hexa (4-amino-3-hydroxyphenoxy) calix [6] arene 47.1g was obtained (yield 84.0%).
The various measured values regarding the obtained compound are shown below. These data indicate that the obtained compound is the target product.
¹ H-NMR (400 MHz, DMSO-d ₆ , ppm): δ0.5-1.5 (54H), δ4.5-5.2 (24H), δ5.8-7.3 (30H), δ8. 4-9.7 (6H)
IR (KBr, / cm): 3361, 3031, 2957, 1581, 1517, 1451
Elemental analysis: [theoretical value] C: 75.81%, H: 7.11%, N: 5.20%, O: 11.88%, [actual value] C: 75.70%, H: 5. 15%

Example 11
5,11,17,23,29,35-Hexa (1,1-dimethylethyl) -37,38,39,40,41,42-hexa (4-amino-3-hydroxyphenoxy) obtained in Example 10 ) Calix [6] arene (1.5 g, 0.93 mmol) and dehydrated N-methylpyrrolidone (8.0 mL) were dissolved in a dry nitrogen atmosphere and then cooled to −10 ° C. Here, 1.4 g (5.8 mmol) of 4-ethynylbenzoic acid chloride was slowly added while taking care not to raise the temperature to 5 ° C. or higher. After the addition, the mixture was stirred at 20 ° C. for 2 hours. The reaction solution was added dropwise to 60 mL of ion exchange water. The precipitated solid was washed twice with 50 mL of methanol, further washed twice with 50 mL of ion-exchanged water, and dried under reduced pressure at 50 ° C. for 2 days to give a brown solid of 5,11,17,23,29,35-hexa. 2.5 g of (1,1-dimethylethyl) -37,38,39,40,41,42-hexa (4- (4-phenylethynyl) benzoylamino-3-hydroxyphenoxy) calix [6] arene was obtained. (Yield 96.0%).
The various measured values regarding the obtained compound are shown below. These data indicate that the obtained compound is the target product.
¹ H-NMR (400 MHz, DMSO-d ₆ , ppm): δ0.5-1.5 (54H), δ4.5-4.9 (12H), δ6.1-6.7 (6H), δ6. 9-8.2 (78H), δ9.5-9.6 (6H), δ9.9-10.1 (6H)
IR (KBr, / cm): 3249, 3033, 2908, 2214, 1642, 1610
Elemental analysis: [theoretical value] C: 81.16%, H: 5.75%, N: 2.96%, O: 10.14%, [actual measured value] C: 82.23%, H: 5. 95%

Example 12
5,11,17,23,29,35-Hexa (1,1-dimethylethyl) -37,38,39,40,41,42-hexa (4- (4-phenylethynyl) obtained in Example 11 ) Benzoylamino-3-hydroxyphenoxy) Calix [6] arene 0.3 g was obtained in the same manner as in Example 3 to obtain an evaluation sample, and the measurement results are summarized in Table 1.

Example 13
In Example 3, an evaluation sample was obtained in the same manner as in Example 3 except that heating at 350 ° C. for 60 minutes was performed at 250 ° C. for 60 minutes, and the measurement results are summarized in Table 1.

Example 14
In Example 3, except that heating at 350 ° C. for 60 minutes was changed to heating at 400 ° C. for 60 minutes, a sample for evaluation was obtained in the same manner as in Example 3, and the measurement results are summarized in Table 1.

Comparative Example 1
In a solution of 12.9 g (122 mmol / unit unit) of poly (hydroxyphenylenemethylene) (Mw3000, Mn980), 36.2 g (146 mmol) of 3-fluoro-6-nitrophenyl benzyl ether and 100 mL of N, N-dimethylformamide, Potassium carbonate 50.0 g (361 mmol) was added. After stirring at 135 ° C. for 12 hours, the reaction solution was filtered. The filtrate was added dropwise to 2000 mL of ion exchange water. The precipitated solid was washed twice with 300 mL of methanol and dried under reduced pressure at 50 ° C. for 2 days to obtain a yellow solid poly ((4-amino-3-hydroxyphenoxy) phenylenemethylene).
The obtained poly ((4-amino-3-hydroxyphenoxy) phenylenemethylene), 4.90 g (4.64 mmol) of 10% palladium on activated carbon, and 90 mL of N, N-dimethylformamide were mixed at room temperature for 36 hours under a hydrogen atmosphere. After stirring, the reaction solution was filtered. The filtrate was added dropwise to 600 mL of ion exchange water. The precipitated solid was washed 3 times with 600 mL of ion-exchanged water and dried under reduced pressure at 50 ° C. for 2 days to give poly ((4-amino-3-hydroxyphenoxy) phenylenemethylene) (Mw5500, Mn1800) as a brown solid. 0 g was obtained.
Further, 2.56 g (12.0 mmol / unit unit) of the obtained poly ((4-amino-3-hydroxyphenoxy) phenylenemethylene) and 20.0 mL of dehydrated N-methylpyrrolidone were dissolved in a dry nitrogen atmosphere. Then, it cooled to -10 degreeC. To this, 3.18 g (13.2 mmol) of phenylethynylbenzoic acid chloride was slowly added, taking care not to raise the temperature above 5 ° C. After the addition, the mixture was stirred at 20 ° C. for 2 hours. The reaction solution was added dropwise to a mixed solution of 50 mL of methanol and 450 mL of ion exchange water. The precipitated solid was washed three times with a mixed solution of 50 mL of methanol and 450 mL of ion-exchanged water, and dried under reduced pressure at 50 ° C. for 2 days, whereby poly ((4- (phenylethynylbenzoyl) amino-3-hydroxyphenoxy of brown solid was obtained. ) Phenylenemethylene) 3.65 g.
Using the obtained polymer, an evaluation sample was obtained in the same manner as in Example 3, and the measurement results are summarized in Table 1.

Comparative Example 2
Instead of using 12.9 g (122 mmol / 1 unit unit) of poly (hydroxyphenylenemethylene) (Mw3000, Mn980) in Comparative Example 1, 26.5 g (122 mmol / 1 unit) of poly (hydroxyphenylenephenylmethylene) (Mw4000, Mn2080) Except for using the unit, in the same manner as in Comparative Example 1, 6.72 g of poly ((4- (phenylethynylbenzoyl) amino-3-hydroxyphenoxy) phenylene phenylmethylene) was obtained as a brown solid.
Using the obtained polymer, an evaluation sample was obtained in the same manner as in Example 3, and the measurement results are summarized in Table 1.

Comparative Example 3
3.296 g (9.0 mmol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was dissolved in 30 mL of dry N-methyl-2-pyrrolidone, and 5-phenylethynyl was added to this solution. 3.032 g (10.0 mmol) of isophthalic acid dichloride was added at 10 ° C. under dry nitrogen. After the addition, the mixture was stirred at 10 ° C. for 1 hour. After stirring, 2.024 g (20.2 mmol) of triethylamine was added at 10 ° C., and then 2.0 g (0.5 mmol) of poly (propylene glycol) bis (2-aminopropyl ether) manufactured by Aldrich was added to 10 mL of γ-butyrolactone. , A number average molecular weight of 4,000) was added at 10 ° C. under dry nitrogen. After the addition, the mixture was stirred at 10 ° C. for 1 hour and then at 20 ° C. for 20 hours. After completion of the reaction, the reaction solution is filtered to remove triethylamine hydrochloride, and the filtered solution is added dropwise to a mixed solution of 1 L of ion exchange water and 0.1 L of isopropanol, and the precipitate is collected and dried. 5.92 g of polymer was obtained. When the molecular weight of the obtained copolymer was determined in terms of polystyrene using GPC manufactured by Tosoh Corporation, the weight average molecular weight was 23,300 and the molecular weight distribution was 2.77. ^{As a result} of measurement by ¹ H-NMR, the introduction ratio of the reactive oligomer component was 21% by weight.
Using the obtained polymer, an evaluation sample was obtained in the same manner as in Example 3, and the measurement results are summarized in Table 1.

Comparative Example 4
In Comparative Example 3, an evaluation sample was obtained in the same manner as in Comparative Example 3 except that heating at 350 ° C. for 60 minutes was performed at 250 ° C. for 60 minutes, and the measurement results are summarized in Table 1.

Comparative Example 5
In Comparative Example 3, an evaluation sample was obtained in the same manner as in Comparative Example 3, except that heating at 350 ° C. for 60 minutes was performed at 400 ° C. for 60 minutes, and the measurement results are summarized in Table 1.

  From the evaluation results of Examples and Comparative Examples summarized in Table 1, the insulating film (coating film) obtained from the insulating film material of the present invention maintains high elastic modulus, high heat resistance, and low water absorption. It can be seen that a low dielectric constant is possible.

    According to the present invention, it is possible to provide an insulating film material and a coating varnish capable of forming an insulating film capable of achieving excellent heat resistance, water absorption and mechanical properties, and further obtaining good electrical properties. Therefore, in fields where such characteristics are required, for example, interlayer insulating films and protective films for semiconductors, interlayer insulating films for multilayer circuits, cover coats for flexible copper-clad plates, solder resist films, liquid crystal alignment films, etc. Can be preferably used.

Claims (20)

  A cyclic aminophenol compound having an aromatic group having a group containing an aminophenol structure in the main chain.   The cyclic aminophenol compound according to claim 1, wherein the group containing an aminophenol structure is an o-aminohydroxyphenoxy group. The cyclic aminophenol compound according to claim 2, wherein the cyclic aminophenol compound has a structure represented by the general formula (1).

(In the formula, Ar represents an aromatic group. X ₁ and X ₂ in the formula are each independently at least one group selected from a hydrogen atom, an aliphatic group, an aromatic group or a sulfonyl group. In the formula, m represents an integer of 3 or more and 20 or less, and n in the formula represents an integer of 1 or more and 3 or less. Show.) The cyclic aminophenol compound according to claim 3, wherein the cyclic aminophenol compound has a group selected from the group represented by the formula (2) as X ₁ and X ₂ in the general formula (1). .

(R ₁ and R ₂ in the formula each independently represent a group selected from the groups represented by formula (3), and may be the same or different from each other. The hydrogen atom may be substituted with at least one group selected from an aliphatic group, an aromatic group and a fluorine atom.)

(The hydrogen atom in the formula may be substituted with at least one group selected from an aliphatic group, an aromatic group and a fluorine atom.) The cyclic aminophenol compound according to claim 4, wherein the cyclic aminophenol compound is a calix resorcalene derivative having at least one of a methyl group and a phenyl group as X ₁ and X ₂ in the general formula (1).   The cyclic aminophenol according to claim 4, wherein the cyclic aminophenol compound is a calix [4] arene derivative or calix [6] arene derivative having one or more t-butyl groups as Ar in the general formula (1). Phenolic compounds.   A cyclic thermosetting resin having an aromatic group having a substituent containing an amidephenol structure having an organic group on carbon of an amide bond in the main chain.   The cyclic thermosetting resin according to claim 7, wherein the substituent containing the amidophenol structure is an o-amidohydroxyphenoxy group. The cyclic thermosetting resin according to claim 7 or 8, wherein the cyclic thermosetting resin has a structure represented by the general formula (4).

(In the formula, Ar represents an aromatic group. X ₁ and X ₂ in the formula are each independently at least one group selected from a hydrogen atom, an aliphatic group, an aromatic group or a sulfonyl group. And R may be the same as or different from each other, R in the formula represents an organic group, m represents an integer of 3 to 20, and n in the formula Represents an integer of 1 to 3.   The cyclic thermosetting resin according to any one of claims 7 to 9, wherein the cyclic thermosetting resin has a group containing an acetylene group as R in the general formula (4). The cyclic thermosetting resin according to claim 10, wherein the cyclic thermosetting resin has a structure represented by the general formula (5).

(In the formula, Ar represents an aromatic group. X ₁ and X ₂ in the formula are each independently at least one group selected from a hydrogen atom, an aliphatic group, an aromatic group or a sulfonyl group. In which Y represents an organic group containing an acetylene group, and m in the formula represents an integer of 3 or more and 20 or less. N in the formula represents an integer of 1 to 3. In the formula, p represents an integer of 1 to 5. The cyclic thermosetting resin according to claim 11, wherein the cyclic thermosetting resin has a structure represented by the general formula (6).

(In the formula, Ar represents an aromatic group. X ₁ and X ₂ in the formula are each independently at least one group selected from a hydrogen atom, an aliphatic group, an aromatic group or a sulfonyl group. And Z may be the same as or different from each other, wherein Z represents a hydrogen group or an organic group, and m represents an integer of 3 or more and 20 or less. (In the formula, n represents an integer of 1 to 3. In the formula, p represents an integer of 1 to 5.) The cyclic thermosetting resin has a group selected from the group represented by the formula (2) as X ₁ and X ₂ in the general formula (4), the general formula (5), or the general formula (6). It is a thing, The cyclic | annular thermosetting resin in any one of Claims 9-12.

(R ₁ and R ₂ in the formula each independently represent a group selected from the groups represented by formula (3), and may be the same or different from each other. The hydrogen atom may be substituted with at least one group selected from an aliphatic group, an aromatic group and a fluorine atom.)

(The hydrogen atom in the formula may be substituted with at least one group selected from an aliphatic group, an aromatic group and a fluorine atom.) A cyclic compound having a structure represented by the general formula (1) is condensed with a carboxylic acid halogen compound or a carboxylic acid ester product to form an amide bond, which is represented by the general formula (4) A method for producing a cyclic thermosetting resin having a structure.

(In the formula, Ar represents an aromatic group. X ₁ and X ₂ in the formula are each independently at least one group selected from a hydrogen atom, an aliphatic group, an aromatic group or a sulfonyl group. In the formula, m represents an integer of 3 or more and 20 or less, and n in the formula represents an integer of 1 or more and 3 or less. Show.)

(In the formula, Ar represents an aromatic group. X ₁ and X ₂ in the formula are each independently at least one group selected from a hydrogen atom, an aliphatic group, an aromatic group or a sulfonyl group. And R may be the same as or different from each other, R in the formula represents an organic group, m represents an integer of 3 to 20, and n in the formula Represents an integer of 1 to 3.   An insulating film material comprising the cyclic thermosetting resin according to claim 7.   An insulating film coating varnish comprising the insulating film material according to claim 15 and an organic solvent capable of dissolving or dispersing the insulating film material.   A resin layer mainly comprising polybenzoxazole obtained by subjecting the insulating film material according to claim 15 or the insulating film coating varnish according to claim 16 to a condensation reaction and a crosslinking reaction by heat treatment. An insulating film comprising:   The insulating film according to claim 17, which is used as an interlayer insulating film for semiconductor multilayer wiring.   The insulating film according to claim 17, which is used as a semiconductor surface protective film.   20. A semiconductor device comprising an interlayer insulating film for multilayer wiring comprising the insulating film according to claim 18 and / or a surface protective layer comprising the insulating film according to claim 19.