JP4495010B2 - Insulating film forming material and insulating film - Google Patents

Description

  The present invention relates to an insulating film used for manufacturing a semiconductor and the like, and relates to an insulating film having excellent heat resistance and mechanical strength and exhibiting a low dielectric constant, a material for forming the insulating film, and a polymer.

  According to Journal of polymer science Part A-1 (1970), 8 (12), p3665-6, polybenzazole containing an adamantane skeleton is known to be useful as a high heat resistant resin. For example, JP 2001-332543 A discloses that, in particular, highly crosslinked polybenzazoles using trifunctional and tetrafunctional adamantane have a number of molecular-level vacancies therein, and thus have a low relative dielectric constant, In addition, since it has mechanical strength and heat resistance, it is disclosed that it is extremely useful as an interlayer insulating film material. These highly crosslinked polybenzazoles can be synthesized by a production method such as heating in the presence of a condensing agent such as polyphosphoric acid, but the obtained highly crosslinked resin has extremely low solubility in a solvent. It is extremely difficult to form a thin film on a substrate by coating or the like, and it is almost impossible to obtain a film thickness necessary as an interlayer insulating film.

  In addition, since tetrafunctional adamantane useful as a raw material monomer has a considerably high polarity, there is a problem that when the coating liquid composed of the monomer is applied onto a substrate, the raw material monomer is likely to be precipitated, resulting in poor coating. .

  In Japanese Patent Application Laid-Open No. 2004-2787, a solution containing an adduct formed by a weak electrical interaction between a tetracarboxylic adamantane derivative that is a Lewis acid and a tetraaminobenzidine acid derivative that is a Lewis base is applied to a plate. Thus, a method for forming a thin film is disclosed. However, when only a tetracarboxylic adamantane derivative, which is a tetrafunctional adamantane, is used as a Lewis acid, a large number of crosslinking points are formed at the time of polymerization, resulting in high density, and since the degree of molecular freedom is reduced, uncrosslinked points are generated. There was a problem of increasing the dielectric constant.

“Journal of polymer science” Part A-1 (1970), 8 (12), p. 3665-6 JP 2001-332543 A Japanese Patent Laid-Open No. 2004-2787

An object of the present invention is to provide an insulating film forming material that has excellent coating properties and can easily form a thin film having a thickness necessary for an interlayer insulating film, and a polymer and an insulating film formed from the material. .
Another object of the present invention is to provide a material capable of forming an insulating film having high heat resistance and low dielectric constant useful for semiconductor parts and the like, and a polymer and an insulating film formed from the material.
Still another object of the present invention is to provide a material capable of forming an insulating film having a high porosity, a polymer formed from the material, and an insulating film.

  As a result of intensive studies to achieve the above object, the present inventors have a plurality of functional groups (groups) that react with each other, and a high molecular weight weight having a pore structure by the reaction of these functional groups (groups). Of the two compounds (monomers) that can form a coalescence, when one compound is used in combination of two or more compounds having different numbers of functional groups (groups), the solubility in a solvent is high and the coatability is improved. The present invention has been completed by finding that it is excellent and that large holes are formed by polymerization and an insulating film having a high porosity can be formed.

（式中、Ｚ ^a は４価のアダマンチル基を示し、Ｒ ¹ 、Ｒ ² 、Ｒ ³ 、Ｒ ⁴ は、同一又は異なって、保護基で保護されていてもよいカルボキシル基又はハロホルミル基を示し、Ｙ ¹ 、Ｙ ² 、Ｙ ³ 、Ｙ ⁴ は、同一又は異なって、単結合又は２価の芳香族性又は非芳香族性環式基を示し、Ｌ ¹ 、Ｌ ³ は、同一又は異なって、水素原子、又は炭化水素基を示す）
であり、［４官能化合物］／［３官能化合物及び／又は２官能化合物］（モル比）が、１０／９０〜９０／１０であり、且つ化合物Ｂが、下記式（８）

（式中、環Ｚ ¹ は単環又は多環の芳香族性又は非芳香族性環を示し、Ｒ ⁵ 、Ｒ ⁶ 、Ｒ ⁷ 、Ｒ ⁸ は環Ｚ ¹ に結合している置換基であって、同一又は異なって、保護基で保護されていてもよいアミノ基、保護基で保護されていてもよいヒドロキシル基、又は保護基で保護されていてもよいメルカプト基を示す。但し、Ｒ ⁵ 、Ｒ ⁶ 、Ｒ ⁷ 、Ｒ ⁸ のうち少なくとも２つは、保護基で保護されていてもよいアミノ基である）
で表されるポリアミン誘導体である絶縁膜形成材料を提供する。
また、本発明は、それぞれの化合物の分子内に２以上の官能基又は官能基群を有しており、一方の化合物の官能基又は官能基群と他方の化合物の官能基又は官能基群との結合により重合して空孔構造を有するポリマーを形成することが可能な２つの化合物Ａ及びＢとの重合反応により得られるポリマーであって、前記化合物Ａが、４官能化合物と３官能化合物及び／又は２官能化合物との組み合わせであり、化合物Ａにおける４官能化合物、３官能化合物、及び２官能化合物が、それぞれ下記式（５）で表されるテトラカルボン酸誘導体、下記式（６）で表されるトリカルボン酸誘導体、及び下記式（７）で表されるジカルボン酸誘導体

（式中、Ｚ ^a は４価のアダマンチル基を示し、Ｒ ¹ 、Ｒ ² 、Ｒ ³ 、Ｒ ⁴ は、同一又は異なって、保護基で保護されていてもよいカルボキシル基又はハロホルミル基を示し、Ｙ ¹ 、Ｙ ² 、Ｙ ³ 、Ｙ ⁴ は、同一又は異なって、単結合又は２価の芳香族性又は非芳香族性環式基を示し、Ｌ ¹ 、Ｌ ³ は、同一又は異なって、水素原子、又は炭化水素基を示す）
であり、［４官能化合物］／［３官能化合物及び／又は２官能化合物］（モル比）が、１０／９０〜９０／１０であり、且つ化合物Ｂが、下記式（８）

（式中、環Ｚ ¹ は単環又は多環の芳香族性又は非芳香族性環を示し、Ｒ ⁵ 、Ｒ ⁶ 、Ｒ ⁷ 、Ｒ ⁸ は環Ｚ ¹ に結合している置換基であって、同一又は異なって、保護基で保護されていてもよいアミノ基、保護基で保護されていてもよいヒドロキシル基、又は保護基で保護されていてもよいメルカプト基を示す。但し、Ｒ ⁵ 、Ｒ ⁶ 、Ｒ ⁷ 、Ｒ ⁸ のうち少なくとも２つは、保護基で保護されていてもよいアミノ基である）
で表されるポリアミン誘導体であるポリマーを提供する。
本発明は、さらに、前記ポリマーからなる絶縁膜を提供する。 That is, the present invention has two or more functional groups or functional group groups in the molecule of each compound, and the functional group or functional group group of one compound and the functional group or functional group group of the other compound An insulating film forming material comprising a polymerizable composition obtained by dissolving two compounds A and B in a solvent, which can be polymerized by bonding of two compounds A and B to form a polymer having a pore structure, Is a combination of a tetrafunctional compound and a trifunctional compound and / or a bifunctional compound, and the tetrafunctional compound, the trifunctional compound, and the bifunctional compound in Compound A are each represented by the following formula (5). Acid derivative, tricarboxylic acid derivative represented by the following formula (6), and dicarboxylic acid derivative represented by the following formula (7)

(In the formula, Z ^a represents a tetravalent adamantyl group, R ¹ , R ² , R ³ and R ⁴ are the same or different and each represents a carboxyl group or a haloformyl group which may be protected with a protective group; Y ¹ , Y ² , Y ³ , Y ⁴ are the same or different and each represents a single bond or a divalent aromatic or non-aromatic cyclic group, and L ¹ and L ³ are the same or different, Represents a hydrogen atom or a hydrocarbon group)
[Tetrafunctional compound] / [trifunctional compound and / or bifunctional compound] (molar ratio) is 10/90 to 90/10, and compound B is represented by the following formula (8):

(In the formula, ring Z ¹ represents a monocyclic or polycyclic aromatic or non-aromatic ring, and R ⁵ , R ⁶ , R ⁷ and R ⁸ are substituents bonded to ring Z ^1. And an amino group which may be protected with a protecting group, a hydroxyl group which may be protected with a protecting group, or a mercapto group which may be protected with a protecting group, provided that R ⁵ is the same or different. , R ⁶ , R ⁷ and R ⁸ are amino groups optionally protected by a protecting group)
An insulating film forming material which is a polyamine derivative represented by the formula:
Further, the present invention has two or more functional groups or functional group groups in the molecule of each compound, and the functional group or functional group group of one compound and the functional group or functional group group of the other compound A polymer obtained by a polymerization reaction of two compounds A and B capable of forming a polymer having a pore structure by polymerizing by bonding, wherein the compound A comprises a tetrafunctional compound, a trifunctional compound, and In combination with a bifunctional compound, the tetrafunctional compound, the trifunctional compound, and the bifunctional compound in the compound A are each represented by a tetracarboxylic acid derivative represented by the following formula (5) and represented by the following formula (6). Tricarboxylic acid derivatives and dicarboxylic acid derivatives represented by the following formula (7)

(In the formula, Z ^a represents a tetravalent adamantyl group, R ¹ , R ² , R ³ and R ⁴ are the same or different and each represents a carboxyl group or a haloformyl group which may be protected with a protective group; Y ¹ , Y ² , Y ³ , Y ⁴ are the same or different and each represents a single bond or a divalent aromatic or non-aromatic cyclic group, and L ¹ and L ³ are the same or different, Represents a hydrogen atom or a hydrocarbon group)
[Tetrafunctional compound] / [trifunctional compound and / or bifunctional compound] (molar ratio) is 10/90 to 90/10, and compound B is represented by the following formula (8):

(In the formula, ring Z ¹ represents a monocyclic or polycyclic aromatic or non-aromatic ring, and R ⁵ , R ⁶ , R ⁷ and R ⁸ are substituents bonded to ring Z ^1. And an amino group which may be protected with a protecting group, a hydroxyl group which may be protected with a protecting group, or a mercapto group which may be protected with a protecting group, provided that R ⁵ is the same or different. , R ⁶ , R ⁷ and R ⁸ are amino groups optionally protected by a protecting group)
The polymer is a polyamine derivative represented by:
The present invention further provides an insulating film made of the polymer.

（式中、Ｚ^aは４価の有機基を示し、Ｒ^a、Ｒ^b、Ｒ^c、Ｒ^dは、同一又は異なって、保護基で保護されていてもよいカルボキシル基、ハロホルミル基、保護基で保護されていてもよいアミノ基、保護基で保護されていてもよいヒドロキシル基、保護基で保護されていてもよいメルカプト基を示し、Ｙ^a、Ｙ^b、Ｙ^c、Ｙ^dは、同一又は異なって、単結合又は２価の芳香族性又は非芳香族性環式基を示し、Ｌ^a、Ｌ^cは、同一又は異なって、水素原子、又は炭化水素基を示す）
で表される化合物であってもよい。前記Ｚ^aは好ましくは４価のアダマンチル基である。 In this specification, in addition to the above-described invention, each compound has two or more functional groups or functional group groups in the molecule, and the functional group or functional group group of one compound and the other compound Insulating film forming material comprising a polymerizable composition obtained by dissolving two compounds A and B in a solvent, which can be polymerized by bonding with a functional group or a functional group to form a polymer having a pore structure The compound A is a combination of a tetrafunctional compound and a trifunctional compound and / or a bifunctional compound, and [tetrafunctional compound] / [trifunctional compound and / or bifunctional compound] (molar ratio) However, the insulating film forming material having 5/95 to 95/5 will also be described. In this insulating film-forming material, tetrafunctional compound constituting the compound A, 3-functional compound, and a bifunctional compound, the following formulas (1), (2), and (3)

(Wherein Z ^a represents a tetravalent organic group, R ^a , R ^b , R ^c and R ^d are the same or different and may be protected with a protecting group, a carboxyl group, a haloformyl group or a protecting group. Represents an amino group which may be protected with, a hydroxyl group which may be protected with a protecting group, a mercapto group which may be protected with a protecting group, and Y ^a , Y ^b , Y ^c and Y ^d are the same Or different, and represents a single bond or a divalent aromatic or non-aromatic cyclic group, and L ^a and L ^c are the same or different and represent a hydrogen atom or a hydrocarbon group)
The compound represented by these may be sufficient. Za is preferably ^a tetravalent adamantyl group.

（式中、環Ｚ^bは単環又は多環の芳香族性又は非芳香族性環を示し、Ｒ^e、Ｒ^f、Ｒ^g、Ｒ^hは環Ｚ^bに結合している置換基であって、同一又は異なって、保護基で保護されていてもよいアミノ基、保護基で保護されていてもよいヒドロキシル基、保護基で保護されていてもよいメルカプト基、又は保護基で保護されていてもよいカルボキシル基を示す）
で表される化合物が挙げられる。 In the insulating film forming material, the compound B is represented by the following formula (4):

(In the formula, ring Z ^b represents a monocyclic or polycyclic aromatic or non-aromatic ring, and R ^e , R ^f , R ^g and R ^h are substituents bonded to ring Z ^b. The amino group may be protected with a protecting group, the hydroxyl group optionally protected with a protecting group, the mercapto group optionally protected with a protecting group, or protected with a protecting group May represent a carboxyl group)
The compound represented by these is mentioned.

In the present specification , each compound has two or more functional groups or functional group groups in the molecule, and the functional group or functional group group of one compound and the functional group or functional group group of the other compound. A polymer obtained by a polymerization reaction with two compounds A and B capable of forming a polymer having a pore structure by polymerization with a bond, wherein the compound A is a tetrafunctional compound, a trifunctional compound and 2 will also be described at least two which is a combination polymer selected from three compounds functional compound.

（式中、Ｚ^aは４価の有機基を示し、Ｒ^a、Ｒ^b、Ｒ^c、Ｒ^dは、同一又は異なって、保護基で保護されていてもよいカルボキシル基、ハロホルミル基、保護基で保護されていてもよいアミノ基、保護基で保護されていてもよいヒドロキシル基、保護基で保護されていてもよいメルカプト基を示し、Ｙ^a、Ｙ^b、Ｙ^c、Ｙ^dは、同一又は異なって、単結合又は２価の芳香族性又は非芳香族性環式基を示し、Ｌ^a、Ｌ^cは、同一又は異なって、水素原子、又は炭化水素基を示す）
で表される化合物が挙げられる。前記Ｚ^aは好ましくは４価のアダマンチル基である。 In the above polymer, as the tetrafunctional compound, trifunctional compound, and bifunctional compound constituting the compound A, the following formulas (1), (2), and (3), respectively:

(Wherein Z ^a represents a tetravalent organic group, R ^a , R ^b , R ^c and R ^d are the same or different and may be protected with a protecting group, a carboxyl group, a haloformyl group or a protecting group. Represents an amino group which may be protected with, a hydroxyl group which may be protected with a protecting group, a mercapto group which may be protected with a protecting group, and Y ^a , Y ^b , Y ^c and Y ^d are the same Or different, and represents a single bond or a divalent aromatic or non-aromatic cyclic group, and L ^a and L ^c are the same or different and represent a hydrogen atom or a hydrocarbon group)
The compound represented by these is mentioned. Za is preferably ^a tetravalent adamantyl group.

（式中、環Ｚ^bは単環又は多環の芳香族性又は非芳香族性環を示し、Ｒ^e、Ｒ^f、Ｒ^g、Ｒ^hは環Ｚ^bに結合している置換基であって、同一又は異なって、保護基で保護されていてもよいアミノ基、保護基で保護されていてもよいヒドロキシル基、保護基で保護されていてもよいメルカプト基、又は保護基で保護されていてもよいカルボキシル基を示す）
で表される化合物が挙げられる。 In the above polymer, the compound B is represented by the following formula (4):

(In the formula, ring Z ^b represents a monocyclic or polycyclic aromatic or non-aromatic ring, and R ^e , R ^f , R ^g and R ^h are substituents bonded to ring Z ^b. The amino group may be protected with a protecting group, the hydroxyl group optionally protected with a protecting group, the mercapto group optionally protected with a protecting group, or protected with a protecting group May represent a carboxyl group)
The compound represented by these is mentioned.

  According to the present invention, since two compounds (monomers) having a functional group (group) that reacts with each other to give a polymer are used, it exhibits high solubility in a solvent, exhibits excellent coating properties, An insulating film having a film thickness necessary for an insulating film can be easily formed. Also, as one of the two compounds, two or more kinds of compounds having different numbers of functional groups (groups) in the molecule are used in combination. A low-density (sparse) pore structure having a long distance and a wide gap can be formed. Therefore, an insulating film having a very low dielectric constant and excellent heat resistance and mechanical strength can be obtained.

  The insulating film forming material of the present invention is composed of a polymerizable composition obtained by dissolving Compound A and Compound B in a solvent. The compound A and the compound B have two or more functional groups or functional group groups in the molecule of each compound, and the functional group or functional group group of one compound and the functional group or functional group of the other compound It is a combination of two compounds that can be polymerized by bonding with a group to form a polymer having a pore structure. In this specification, the case of having two functional groups or groups of functional groups involved in bonding (polymerization reaction) is “bifunctional”, the case of having three is “trifunctional”, and the case of having four is “tetrafunctional” May be called.

  The central skeleton of compound A and compound B can be composed of carbon atoms, oxygen atoms, silicon atoms, nitrogen atoms, sulfur atoms, etc., and the number of constituent atoms is usually 100 or less. Moreover, the molecular weight of the compound A and the compound B is, for example, about 50 to 1500, and preferably about 100 to 1000.

  As a combination of compounds A and B capable of forming a polymer having a pore structure, for example, a plurality of (for example, 2 to 4) functional groups or functional groups bonded to the central skeleton have a two-dimensional structure or a three-dimensional structure. Compound A and a plurality of (for example, 2 to 4, preferably 2) functional groups or functional groups bonded to the central skeleton have a one-dimensional structure (linear) or a two-dimensional structure (linear with an angle) And a combination with the compound B forming In this case, the compound A forms a nodal point or a cross-linking point (vertex) of the polymer, and the compound B forms a connecting portion (side) connecting the nodal points or cross-linking points. Holes are formed at sites surrounded by some nodes or bridge points and some connections. The polymer constitutes a polymer (polymer crosslinked product) having a branched structure (particularly a multi-branched structure), but may have a chain structure that does not partially have a branch.

  In the present invention, the compound A is composed of a combination of a tetrafunctional compound and a trifunctional compound and / or a bifunctional compound, and [tetrafunctional compound] / [trifunctional compound and / or bifunctional compound] (molar ratio). ) Is 5/95 to 95/5, preferably about 10/90 to 90/10. As the “combination of a tetrafunctional compound and a trifunctional compound and / or a bifunctional compound”, for example, two combinations of a tetrafunctional compound and a trifunctional compound, two combinations of a tetrafunctional compound and a bifunctional compound, Three combinations of a tetrafunctional compound, a trifunctional compound, and a bifunctional compound are mentioned. These compounds constituting the compound A may be a plurality of compounds as the compounds having the same number of functional groups (groups) in the molecule.

  In the present invention, the tetrafunctional compound alone reduces the degree of molecular freedom by cross-linking and easily generates an uncrosslinked functional group. However, in the present invention, as the compound A, the tetrafunctional compound and the bifunctional compound and / or the trifunctional compound are used in the above ratio. Therefore, there is an effect that the degree of molecular freedom is increased and the degree of crosslinking is improved. Further, when the tetrafunctional compound is used at a higher ratio than the other compounds, the tetrafunctional compound / the other compound (molar ratio) is in a range of 51/49 to 90/10, and thus a highly branched structure. It is preferable because the formation of a molecular crosslinked body is facilitated. The ratio of the trifunctional compound and the bifunctional compound as a compound combined with the tetrafunctional compound is such that [trifunctional compound] / [bifunctional compound] (molar ratio) is, for example, 100/0 to 0/100, preferably It is about 90/10 to 10/90.

  Examples of the central skeleton of compound A in the above case include non-aromatic ring skeletons (bridged skeletons) such as an adamantane skeleton, a tetraphenyladamantane skeleton, a norbornane skeleton, a tetramethylnorbornane skeleton, a norbornene skeleton, and a tetramethylnorbornene skeleton. A skeleton having a carbon atom such as a tetraphenylmethane skeleton; a skeleton having a two-dimensional structure such as a porphyrin skeleton; a chain skeleton such as a butane skeleton (for example, a chain carbonization having about 4 to 10 carbon atoms) Hydrogen skeleton, etc.). The molecular weight of the central skeleton portion of Compound A is, for example, about 40 to 1460. In addition, examples of the central skeleton of compound B include monocyclic or polycyclic aromatic or non-aromatic ring skeletons such as a benzene ring and a biphenyl ring.

  The functional group is not particularly limited as long as it has reactivity, but representative examples include a carboxyl group, amino group, hydroxyl group, mercapto group, silanol group, halogen atom, carbanion, or these. Groups and the like. In addition, these groups may be derivatized into reactive groups and may be protected with a protecting group. Examples of the reactive group include a haloformyl group, an acid anhydride group (which can also be classified as a carboxyl group protected by a protecting group) and the like in the carboxyl group. As the protecting group, a protecting group conventionally used in the field of organic synthesis can be used.

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

As a typical example of the compound constituting the compound A, the tetrafunctional compound represented by the formula (1), the trifunctional compound represented by the formula (2) and / or the formula (3) And a combination with a bifunctional compound. In formulas (1) to (3), Za represents ^a tetravalent organic group, and R ^a , R ^b , R ^c , and R ^d are the same or different and may be protected by a protecting group. , A haloformyl group, an amino group that may be protected with a protecting group, a hydroxyl group that may be protected with a protecting group, and a mercapto group that may be protected with a protecting group, Y ^a , Y ^b , Y ^c Y ^d is the same or different and represents a single bond or a divalent aromatic or non-aromatic cyclic group, and L ^a and L ^c are the same or different and represent a hydrogen atom or a hydrocarbon group. Show. In this compound, a carboxyl group protected with a protecting group, a haloformyl group, an amino group optionally protected with a protecting group, a hydroxyl group optionally protected with a protecting group, or a mercapto optionally protected with a protecting group The group corresponds to the functional group or the functional group group.

Examples of the organic group in Z ^a tetravalent aromatic or nonaromatic cyclic group, tetravalent acyclic groups, and tetravalent group to which it is multiple bond. The aromatic ring constituting the tetravalent aromatic cyclic group includes a plurality of aromatic heterocyclic rings such as aromatic carbon rings such as benzene rings and pyrrole rings, single bonds, or divalent hydrocarbon groups ( A methylene group, a vinylene group, etc.), a polycycle (for example, porphyrin ring etc.) etc. couple | bonded through 1 or 2 or more coupling groups, such as an oxygen atom, a nitrogen atom, a silicon atom, and a sulfur atom. As the non-aromatic ring constituting the tetravalent non-aromatic cyclic group, a monocyclic or polycyclic (bridged) alicyclic carbocyclic ring or non-aromatic heterocyclic ring (for example, an adamantane ring, Norbornane ring, norbornene ring, etc.). Examples of the tetravalent acyclic group include chain atoms such as a carbon atom; butane-1,2,3,4-tetrayl group and 2,3-dimethylbutane-1,2,3,4-tetrayl group. A hydrocarbon group etc. are mentioned. Of these, ^a tetravalent adamantyl group, particularly an adamantyl group (1,3,5,7-adamantanetetrayl group) having binding sites at four bridgehead positions is preferably used as Za.

Examples of the “protecting group” of the carboxyl group which may be protected with a protecting group in R ^a , R ^b , R ^c and R ^d include, for example, an alkoxy group (methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, s - butoxy, t-butoxy, C _1-10 alkoxy groups such as hexyloxy; methoxymethyloxy, etc. (C _1-4 alkoxy) _1-2 C _1-4 alkoxy groups such as methoxyethoxymethyl group), a cycloalkyl Oxy groups (C _3-20 cycloalkyloxy groups such as cyclopentyloxy and cyclohexyloxy), tetrahydrofuranyloxy groups, tetrahydropyranyloxy groups, aryloxy groups (C _6-20 aryloxy groups such as phenoxy and methylphenoxy groups) ), Aralkyloxy group (benzyloxy, diphenylmethyloxy group) Which C _7-18 aralkyloxy group), trialkylsilyl group (trimethylsilyl oxy, tri C _1-4 alkylsilyl group such as triethylsilyl group), an optionally substituted amino group (an amino group; Mono- or di-substituted C _1-6 alkylamino groups such as methylamino, dimethylamino, ethylamino and diethylamino; cyclic amino groups such as pyrrolidino and piperidino groups), hydrazino groups which may have a substituent [hydrazino group, N - C ₇ such as a phenyl hydrazino group, (such as C _1-10 alkoxycarbonyl hydrazino group such as t- butoxycarbonyl hydrazino group) alkoxycarbonyl hydrazino group, an aralkyloxycarbonyl hydrazino group (benzyloxycarbonyl hydrazino group _-18 aralkyloxycarbonylhydrazino group)], Examples include acyloxy groups (C _1-10 acyloxy groups such as acetoxy and propionyloxy groups), acyl groups (C _1-10 acyl groups such as acetyl and propionyl groups), and the like. The protecting group for the carboxyl group is not limited to these, and other protecting groups used in the field of organic synthesis can also be used.

Preferred examples of the carboxyl group protected by a protecting group include C _1-6 alkoxy-carbonyl group, (C _1-4 alkoxy) _1-2 -C _1-4 alkoxy-carbonyl group, N-substituted carbamoyl group, tetrahydro A pyranyloxycarbonyl group, a tetrahydrofuranyloxycarbonyl group, an aryloxycarbonyl group, and a trialkylsilyloxycarbonyl group are included.

As the haloformyl group (halogenated carbonyl group) in R ^a , R ^b , R ^c and R ^d , a chloroformyl group (carbonyl chloride group), a bromoformyl group (carbonyl bromide group), a fluoroformyl group (carbonyl fluoride group) And iodoformyl group (carbonyl iodide group).

Examples of the “protecting group” of the amino group which may be protected with a protecting group in R ^a , R ^b , R ^c and R ^d include, for example, an acyl group (formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, pivaloyl group) C _1-6 aliphatic acyl group such as; benzoyl, and other aromatic acyl groups each having about 6 to 20 carbon atoms, such as naphthoyl group), alkoxycarbonyl groups (methoxycarbonyl, ethoxycarbonyl, such as t- butoxycarbonyl C _{1- 4} alkoxy-carbonyl groups), aralkyloxy-carbonyl groups (benzyloxycarbonyl groups, C _7-20 aralkyloxycarbonyl groups such as p-methoxybenzyloxycarbonyl groups), alkylidene groups (methylidene, ethylidene, propylidene, isopropylidene, Butylidene, isobutylidene, pentilidene Cyclopentylidene, Hekiriden, aliphatic alkylidene group such as cyclohexylidene group; benzylidene and aromatic alkylidene group such as methyl phenyl methylidene) and the like. The amino-protecting group is not limited to these, and those commonly used in the field of organic synthesis can be used.

  Further, the amino group which may be protected with a protecting group includes a mono-substituted amino group as long as the properties of the reaction and the final polymer crosslinked product are not impaired. Examples of mono-substituted amino groups include alkylamino groups such as methylamino group, ethylamino group, propylamino group, butylamino group and t-butylamino group; cycloalkylamino groups such as cyclohexylamino group; phenylamino group and the like An arylamino group such as benzylamino group, and the like.

Examples of the “protecting group” of the hydroxyl group which may be protected with a protecting group in R ^a , R ^b , R ^c and R ^d and the mercapto group which may be protected with a protecting group include an alkyl group (methyl, C _1-6 alkyl groups such as ethyl, propyl, isopropyl, butyl, t-butyl, pentyl and hexyl groups), cycloalkyl groups (3- to 15-membered cycloalkyl groups such as cyclopentyl and cyclohexyl groups), aralkyl groups (C _7-20 aralkyl group such as benzyl group), substituted methyl group (substituted methyl group having about 2 to 10 total carbon atoms such as methoxymethyl, benzyloxymethyl, t-butoxymethyl, 2-methoxyethoxymethyl group) Substituted ethyl groups (1-ethoxyethyl, 1-methyl-1-methoxyethyl group, etc.), acyl groups (formyl, acetyl, propionyl) C _4-20 alicyclic acyl group such as a cyclohexyl group; butyryl, isobutyryl, valeryl, an aliphatic acyl group of C _1-10, such as pivaloyl group benzoyl and C _7-20 aromatic acyl group such as a naphthoyl group ), an alkoxycarbonyl group (methoxycarbonyl, ethoxycarbonyl, C _1-4 alkoxy, such as t- butoxycarbonyl - carbonyl group), C ₇ such aralkyloxycarbonyl groups (benzyloxycarbonyl group, p- methoxybenzyloxycarbonyl group _-20 aralkyloxy-carbonyl group) and the like. The protecting group for the hydroxyl group and mercapto group is not limited to these, and those commonly used in the field of organic synthesis can be used.

The aromatic ring corresponding to the divalent aromatic cyclic group in Y ^a , Y ^b , Y ^c and Y ^d includes a monocyclic or polycyclic aromatic carbocyclic ring and aromatic heterocyclic ring. In the present specification, the term “polycycle” refers to a condensed ring structure in which two adjacent rings share two or more atoms, and two or more rings are a single bond or a divalent hydrocarbon group. (Methylene group, vinylene group, etc.), used to mean including those having a structure bonded through one or more linking groups such as oxygen atom, nitrogen atom, silicon atom, sulfur atom and the like.

  Examples of the monocyclic aromatic hydrocarbon ring include a benzene ring. The polycyclic aromatic hydrocarbon ring has, for example, a condensed ring structure in which two or more aromatic rings such as naphthalene ring, anthracene ring, phenanthrene ring, triphenylene ring, pyrene ring each share two or more atoms. And those having a structure in which two or more aromatic rings such as a biphenyl ring, a biphenylene ring, a fluorene ring, and a stilbene ring are bonded via a linking group such as a single bond. Examples of the aromatic heterocycle include monocyclic or polycyclic aromatic heterocycles containing one or more heteroatoms such as oxygen atom, sulfur atom and nitrogen atom. Specific examples of the aromatic heterocyclic ring include a monocyclic ring such as a furan ring, a thiophene ring, a pyridine ring, and a picoline ring; a polycyclic ring such as a quinoline ring, an isoquinoline ring, an acridine ring, and a phenazine ring. These rings may have a substituent as long as the properties of the reaction and the crosslinked polymer are not impaired.

Non-aromatic rings corresponding to the divalent non-aromatic cyclic group in Y ^a , Y ^b , Y ^c and Y ^d include monocyclic or polycyclic alicyclic carbocycles and non-aromatic heterocycles. Includes a ring. As the alicyclic carbocycle, a cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cyclooctane ring and the like having about 3 to 20 members (preferably 3 to 15 members, more preferably 3 to 12 members) are used. Alkane ring; monocyclic alicyclic such as cycloalkene ring of about 3 to 20 members (preferably 3 to 15 members, more preferably 3 to 10 members) such as cyclopropene ring, cyclobutene ring, cyclopentene ring and cyclohexene ring Carbocyclic ring: adamantane ring, perhydroindene ring, decalin ring, perhydrofluorene ring, perhydroanthracene ring, perhydrophenanthrene ring, tricyclodecane ring, tricycloundecane ring, tetracyclododecane ring, perhydroacenaphthene ring, Perhydrophenalene ring, norbornane ring, norbornene ring, etc. 2 Such as about 6 ring bridged cyclic carbon ring. Examples of the non-aromatic heterocycle include a 5- or 6-membered heterocycle having at least one heteroatom selected from an oxygen atom, a sulfur atom and a nitrogen atom, and a condensed ring containing these. The non-aromatic cyclic group may have a substituent as long as it does not impair the properties of the reaction or the crosslinked polymer.

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

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

The hydrocarbon group in which an aliphatic hydrocarbon group and an alicyclic hydrocarbon group are bonded includes a cycloalkyl-alkyl group such as cyclopentylmethyl, cyclohexylmethyl, 2-cyclohexylethyl group (for example, C _3-20 cycloalkyl- C _1-4 alkyl group and the like). The hydrocarbon group in which an aliphatic hydrocarbon group and an aromatic hydrocarbon group are bonded to each other includes an aralkyl group (for example, a C _7-18 aralkyl group) and an alkyl-substituted aryl group (for example, about 1 to about 4). A phenyl group substituted with a C _1-4 alkyl group or a naphthyl group).

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

  As typical examples of the tetrafunctional compound represented by the formula (1), for example, a benzene derivative having a benzene ring as a central skeleton such as pyromellitic acid; 1,3,5,7-adamantanetetracarboxylic acid, 1, Adamantane derivatives having an adamantane ring as a central skeleton such as 3,5,7-tetrakis (4-carboxyphenyl) adamantane and 1,3,5,7-adamantanetetraamine; 2,3,5,6-norbornanetetracarboxylic acid 2,3,5,6-norbornenetetracarboxylic acid, 2,3,5,6-tetrakis (hydroxymethyl) norbornane, norbornane ring or norbornene ring such as 2,3,5,6-tetrakis (hydroxymethyl) norbornene A norbornane or norbornene derivative having a central skeleton; tetrakis (4-carboxypheny ) Tetraarylmethane derivatives having carbon atoms such as methane in the central skeleton; Butane derivatives having butane skeleton as the central skeleton such as erythritol; Porphyrin derivatives having a porphyrin ring having a functional group in four nitrogen-containing rings of porphyrin as the central skeleton Etc. Specific examples of the tetrafunctional compound include a polycarboxylic acid derivative represented by the following formula (5). These tetrafunctional compounds can be used alone or in combination of two or more.

  As a typical example of the trifunctional compound represented by the formula (2), for example, a typical example of the tetrafunctional compound includes a compound having the same skeleton as the above exemplified compound and having three functional groups. It is done. Specific examples of the trifunctional compound include a polycarboxylic acid derivative represented by the following formula (6). These trifunctional compounds can be used alone or in combination of two or more.

  As a typical example of the bifunctional compound represented by the formula (3), for example, a typical example of the tetrafunctional compound is a compound having the same skeleton as the above exemplified compound and having two functional groups. It is done. Specific examples of the bifunctional compound also include a polycarboxylic acid derivative represented by the following formula (7). These bifunctional compounds can be used alone or in combination of two or more.

As the structure of the compounds represented by the formulas (1) to (3), a sterically bulky structure (a structure having a large volume) is preferable. Particularly, tetrafunctional compounds of formula (1) is centered on the ^{Z a, R a, R b} , R c, is preferably a structure of substantially tetrahedral whose vertices R ^d, formula (2) trifunctional compounds, centered on the Z ^a, vertex ^{L a, R b, R c} , preferably a structure of substantially regular triangular pyramid to the bottom surface of R ^d. Further, the bifunctional compound of the formula (3) preferably has a structure in which R ^a and R ^c are substantially symmetrical with Z ^a as the center.

In the insulating film forming material of the present invention, preferably, the compound A is a tetracarboxylic acid derivative represented by the above (5), a tricarboxylic acid derivative represented by the above formula (6) and / or the above formula (7). It is comprised by the combination which consists of two types of polycarboxylic acid derivatives with the dicarboxylic acid derivative represented. In the present specification, ^a compound in which ^a carboxyl group that may be protected with a protecting group is not directly bonded to Za is also referred to as a polycarboxylic acid derivative for convenience.

Equation (5), (6), tetravalent organic groups in Z ^a (7) has the formula (1), (2) is the same as the tetravalent organic group represented by Z ^a in (3). The carboxyl group and haloformyl group which may be protected with a protecting group in R ¹ , R ² , R ³ and R ⁴ are the same as the carboxyl group and haloformyl group which may be protected with a protecting group in R ^a and the like. . The divalent aromatic or non-aromatic cyclic group for Y ¹ , Y ² , Y ³ and Y ⁴ is the same as the divalent aromatic or non-aromatic cyclic group for Y ^a . Further, the hydrocarbon group of L ^1, L ³ is the same as the hydrocarbon group in R ^a and the like.

The polycarboxylic acid derivatives represented by the formulas (5), (6), and (7) are polycarboxylic acid esters when R ^{1 to} R ⁴ are alkoxycarbonyl groups, aryloxycarbonyl groups, and the like, and R ¹ to R ⁴ When R ⁴ is an optionally substituted carbamoyl group, it is a polycarboxylic acid amide, and when R ^{1 to} R ⁴ are haloformyl groups, it is a polycarboxylic acid halide.

Preferred R ^{1 to} R ⁴ include a carboxyl group, a C _1-6 alkoxy-carbonyl group, (C _1-4 alkoxy) _1-2 -C _1-4 alkoxy-carbonyl group, an N-substituted carbamoyl group, tetrahydropyranyl. An oxycarbonyl group, a tetrahydrofuranyloxycarbonyl group, an aryloxycarbonyl group, a trialkylsilyloxycarbonyl group, and a haloformyl group are included.

The tetracarboxylic acid derivative (tetracarboxylic acid and its derivatives) represented by the formula (5) includes a compound in which all four functional groups of R ¹ , R ² , R ³ and R ⁴ are carboxyl groups, one functional group A compound in which the group is a carboxyl group or haloformyl group protected with a protecting group, a compound in which two functional groups are a carboxyl group or haloformyl group protected in a protecting group, and a carboxyl group in which three functional groups are protected with a protecting group Or a compound that is a haloformyl group, and a compound that is a carboxyl group or a haloformyl group in which all four functional groups are protected with a protecting group.

Representative examples of the tetracarboxylic acid derivative represented by the formula (5), the exemplified compound Z ^a is a tetravalent adamantane methyl group, 1,3,5,7-adamantane tetracarboxylic acid, 1, 3,5,7-tetrakis (4-carboxyphenyl) adamantane; 1-methoxycarbonyl-3,5,7-adamantane tricarboxylic acid, 1- (t-butoxycarbonyl) -3,5,7-adamantane tricarboxylic acid, 1 -Tetrahydropyranyl (THP) oxycarbonyl-3,5,7-adamantane tricarboxylic acid, 1-phenoxycarbonyl-3,5,7-adamantane tricarboxylic acid, 1-methoxymethyl (MEM) oxycarbonyl-3,5,7 -Adamantanetricarboxylic acid, 1-trimethylsilyl (TMS) oxycarbonyl-3,5,7 Adamantanetricarboxylic acid, 1,3,5-tricarboxy-7-adamantanecarboxylic acid chloride, 1-diethylcarbamoyl-3,5,7-adamantanetricarboxylic acid, 1- (1-pyrrolidinylcarbonyl) -3,5 7-adamantane tricarboxylic acid, 1,3,5-tris (4-carboxyphenyl) -7- (4-methoxycarbonylphenyl) adamantane; 1,3-bis (methoxycarbonyl) -5,7-adamantane dicarboxylic acid, 1 , 3-bis (t-butoxycarbonyl) -5,7-adamantanedicarboxylic acid, 1,3-bis (tetrahydropyranyloxycarbonyl) -5,7-adamantanedicarboxylic acid, 1,3-bis (phenoxycarbonyl)- 5,7-adamantane dicarboxylic acid, 1,3-bis (methoxymethylo Xoxycarbonyl) -5,7-adamantane dicarboxylic acid, 1,3-bis (trimethylsilyloxycarbonyl) -5,7-adamantane dicarboxylic acid, 1,3-dicarboxy-5,7-adamantane dicarboxylic acid dichloride, 1,3 -Bis (diethylcarbamoyl) -5,7-adamantane dicarboxylic acid, 1,3-bis (1-pyrrolidinylcarbonyl) -5,7-adamantane dicarboxylic acid, 1,3-bis (4-carboxyphenyl) -5 , 7-bis (4-methoxycarbonylphenyl) adamantane; 1,3,5-tris (methoxycarbonyl) -7-adamantane monocarboxylic acid, 1,3,5-tris (t-butoxycarbonyl) -7-adamantane mono Carboxylic acid, 1,3,5-tris (tetrahydropyranyloxycarbonyl) -7 Adamantane monocarboxylic acid, 1,3,5-tris (phenoxycarbonyl) -7-adamantane monocarboxylic acid, 1,3,5-tris (methoxymethyloxycarbonyl) -7-adamantane monocarboxylic acid, 1,3,5 -Tris (trimethylsilyloxycarbonyl) -7-adamantane monocarboxylic acid, 1-carboxy-3,5,7-adamantane tricarboxylic acid trichloride, 1,3,5-tris (diethylcarbamoyl) -7-adamantane monocarboxylic acid, 1 , 3,5-tris (1-pyrrolidinylcarbonyl) -7-adamantane monocarboxylic acid, 1- (4-carboxyphenyl) -3,5,7-tris (4-methoxycarbonylphenyl) adamantane; , 5,7-tetrakis (methoxycarbonyl) adamantane, , 3,5,7-tetrakis (t-butoxycarbonyl) adamantane, 1,3,5,7-tetrakis (tetrahydropyranyloxycarbonyl) adamantane, 1,3,5,7-tetrakis (phenoxycarbonyl) adamantane, , 3,5,7-tetrakis (methoxymethyloxycarbonyl) adamantane, 1,3,5,7-tetrakis (trimethylsilyloxycarbonyl) adamantane, 1,3,5,7-adamantanetetracarboxylic acid tetrachloride, 1,3 , 5,7-tetrakis (diethylcarbamoyl) adamantane, 1,3,5,7-tetrakis (1-pyrrolidinylcarbonyl) adamantane, 1,3,5,7-tetrakis (4-methoxycarbonylphenyl) adamantane, etc. Can be mentioned.

  These tetracarboxylic acids or derivatives thereof can be used alone or in combination of two or more.

  The tricarboxylic acid derivative represented by the formula (6) (tricarboxylic acid and derivatives thereof) is a compound in which all three functional groups are carboxyl groups, one functional group is a carboxyl group protected by a protecting group or a haloformyl group. Compounds, compounds in which two functional groups are carboxyl groups or haloformyl groups protected with protecting groups, and compounds in which all three functional groups are carboxyl groups or haloformyl groups protected with protecting groups are included.

As a typical example of the tricarboxylic acid derivative represented by the formula (6), a compound in which Z ^a is a tetravalent adamantane group is exemplified by 7-methyl-1,3,5-adamantanetricarboxylic acid, 7- Phenyl-1,3,5-adamantanetricarboxylic acid, 1,3,5-tris (4-carboxyphenyl) adamantane, 1,3,5-tris (4-carboxyphenyl) -7-methyladamantane, 1,3, 5-tris (4-carboxyphenyl) -7-phenyladamantane; 1-methoxycarbonyl-3,5-adamantane dicarboxylic acid, 1- (t-butoxycarbonyl) -3,5-adamantane dicarboxylic acid, 1-tetrahydropyranyl Oxycarbonyl-3,5-adamantane dicarboxylic acid, 1-phenoxycarbonyl-3,5-adamantane Carboxylic acid, 1-methoxymethyloxycarbonyl-3,5-adamantane dicarboxylic acid, 1-trimethylsilyloxycarbonyl-3,5-adamantane dicarboxylic acid, 1,3-dicarboxy-5-adamantanecarboxylic acid chloride, 1-diethylcarbamoyl -3,5-adamantane dicarboxylic acid, 1-pyrrolidinylcarbonyl-3,5-adamantane dicarboxylic acid, 1,3-bis (4-carboxyphenyl) -5- (4-methoxycarbonylphenyl) adamantane; 1,3 -Bis (methoxycarbonyl) -5-adamantane monocarboxylic acid, 1,3-bis (t-butoxycarbonyl) -5-adamantane monocarboxylic acid, 1,3-bis (tetrahydropyranyloxycarbonyl) -5-adamantane mono Carboxylic acid, 1,3-bis ( Phenoxycarbonyl) -5-adamantane monocarboxylic acid, 1,3-bis (methoxymethyloxycarbonyl) -5-adamantane monocarboxylic acid, 1,3-bis (trimethylsilyloxycarbonyl) -5-adamantane monocarboxylic acid, 1- Carboxy-3,5-adamantane dicarboxylic acid dichloride, 1,3-bis (diethylcarbamoyl) -5-adamantane monocarboxylic acid, 1,3-bis (1-pyrrolidinylcarbonyl) -5-adamantane monocarboxylic acid, 1 -(4-carboxyphenyl) -3,5-bis (4-methoxycarbonylphenyl) -adamantane; 1,3,5-tris (methoxycarbonyl) adamantane, 1,3,5-tris (t-butoxycarbonyl) adamantane 1,3,5-tris (tetrahydropyra Ruoxycarbonyl) adamantane, 1,3,5-tris (phenoxycarbonyl) adamantane, 1,3,5-tris (methoxymethyloxycarbonyl) adamantane, 1,3,5-tris (trimethylsilyloxycarbonyl) adamantane, 1, 3,5-adamantanetricarboxylic acid trichloride, 1,3,5-tris (diethylcarbamoyl) adamantane, 1,3,5-tris (1-pyrrolidinylcarbonyl) adamantane, 1,3,5-tris (4-methoxy) Carbonylphenyl) adamantane and the like.

  These tricarboxylic acids or derivatives thereof can be used alone or in combination of two or more.

  The dicarboxylic acid derivative (dicarboxylic acid and its derivative) represented by the formula (7) is a compound in which all two functional groups are carboxyl groups, one functional group is a carboxyl group protected with a protecting group or a haloformyl group. Compounds, compounds in which all two functional groups are carboxyl groups or haloformyl groups protected with protecting groups are included.

Representative examples of the dicarboxylic acid derivative represented by the formula (7), the exemplified compound Z ^a is a tetravalent adamantane methyl group, 1,3-adamantane dicarboxylic acid, 5-methyl-1,3 Adamantanedicarboxylic acid, 5-phenyl-1,3-adamantanedicarboxylic acid, 1,3-bis (4-carboxyphenyl) adamantane, 1,3-bis (4-carboxyphenyl) -5-methyladamantane, 1,3- Bis (4-carboxyphenyl) -5-phenyladamantane; 1-methoxycarbonyl-3-adamantane monocarboxylic acid, 1- (t-butoxycarbonyl) -3-adamantane monocarboxylic acid, 1-tetrahydropyranyloxycarbonyl-3 -Adamantane monocarboxylic acid, 1-phenoxycarbonyl-3-adamantane monocar Acid, 1-methoxymethyloxycarbonyl-3-adamantane monocarboxylic acid, 1-trimethylsilyloxycarbonyl-3-adamantane monocarboxylic acid, 1-carboxy-3-adamantanecarboxylic acid chloride, 1-diethylcarbamoyl-3-adamantane mono Carboxylic acid, 1-pyrrolidinylcarbonyl-3-adamantane monocarboxylic acid, 1- (4-carboxyphenyl) -3- (4-methoxycarbonylphenyl) adamantane; 1,3-bis (methoxycarbonyl) adamantane, 1, 3-bis (t-butoxycarbonyl) adamantane, 1,3-bis (tetrahydropyranyloxycarbonyl) adamantane, 1,3-bis (phenoxycarbonyl) adamantane, 1,3-bis (methoxymethyloxycarbonyl) adaman 1,3-bis (trimethylsilyloxycarbonyl) adamantane, 1,3-adamantanedicarboxylic acid dichloride, 1,3-bis (diethylcarbamoyl) adamantane, 1,3-bis (1-pyrrolidinylcarbonyl) adamantane, , 3-bis (4-methoxycarbonylphenyl) adamantane and the like.

  These dicarboxylic acids or derivatives thereof can be used alone or in combination of two or more.

  The polycarboxylic acid derivatives represented by the above formulas (5), (6) and (7) can be prepared by known methods, known organic synthesis reactions, known methods for introducing protecting groups to carboxyl groups (for example, esters) Etc.) and the like.

In the insulating film forming material of the present invention, a typical example of the compound B includes a compound represented by the formula (4). In formula (4), ring Z ^b represents a monocyclic or polycyclic aromatic or non-aromatic ring, and R ^e , R ^f , R ^g and R ^h are substituents bonded to ring Z ^b. And the same or different, an amino group which may be protected with a protecting group, a hydroxyl group which may be protected with a protecting group, a mercapto group which may be protected with a protecting group, or a protective group The carboxyl group which may be made is shown. In this compound, R ^e , R ^f , R ^g , and R ^h correspond to the functional group or functional group group.

R ^e, R ^f, a pair of groups of R ^g, R ^h (e.g., R ^e and R ^f, R ^g and R ^h), from the viewpoint of ease of cyclization, respectively, the constituent atoms of the ring Z ^b Are preferably bonded to the positions of 1, 2 (α position) or 1, 3 (β position). The pair of groups is preferably a combination of two amino groups, an amino group and a hydroxyl group, an amino group and a mercapto group, and two carboxyl groups. The compound B having such a pair of groups can form a ring with the compound A having one carboxyl group or two amino groups as a functional group or a functional group group.

The monocyclic or polycyclic aromatic ring in the ring Z ^b include aromatic carbocyclic and aromatic heterocyclic. A benzene ring is mentioned as a monocyclic aromatic carbocyclic ring. Examples of polycyclic aromatic carbocycles include those having a condensed ring structure in which two or more aromatic rings such as naphthalene ring, anthracene ring, phenanthrene ring, triphenylene ring, pyrene ring each share two or more atoms Two or more aromatic rings such as a biphenyl ring, a biphenylene ring, a fluorene ring, and a stilbene ring are one or more linking groups [eg, single bond, divalent hydrocarbon group (methylene group, vinylene group, etc.), oxygen Atoms, nitrogen atoms, silicon atoms, sulfur atoms, etc.]. Examples of the aromatic heterocycle include monocyclic or polycyclic aromatic heterocycles containing one or more heteroatoms such as oxygen atom, sulfur atom and nitrogen atom. Specific examples of the aromatic heterocyclic ring include a monocyclic ring such as a furan ring, a thiophene ring, a pyridine ring, and a picoline ring; a polycyclic ring such as a quinoline ring, an isoquinoline ring, an acridine ring, and a phenazine ring.

The monocyclic or polycyclic non-aromatic ring in the ring Z ^b includes an alicyclic hydrocarbon ring and a non-aromatic heterocyclic ring. Examples of the non-aromatic ring include ^a non-aromatic ring corresponding to the non-aromatic cyclic group in Za. The monocyclic or polycyclic aromatic or non-aromatic ring in the ring Z ^b may have a substituent as long as the physical properties of the reaction and the crosslinked polymer are not impaired.

Examples of the “protecting group” of the amino group which may be protected with a protecting group in R ^e , R ^f , R ^g and R ^h include the protecting group for the amino group in the aforementioned R ^a , R ^b , R ^c and R ^d . The same thing is mentioned. In addition, as a protecting group for an amino group, a protecting group that can simultaneously protect a plurality of amino groups (polyfunctional protecting group) can also be used. Such protecting groups include, for example, carbonyl group, oxalyl group, butane-2,3-diylidene group and the like. When such a protecting group is used, two of R ^e , R ^f , R ^g and R ^h are simultaneously protected by one polyfunctional protecting group, and the ring adjacent to ring Z ^b is It is formed. In addition, the amino group which may be protected with a protecting group for R ^e , R ^f , R ^g and R ^h includes a mono-substituted amino group as long as it does not impair the physical properties of the reaction and the final polymer crosslinked product. included. Examples of mono-substituted amino groups include alkylamino groups such as methylamino group, ethylamino group, propylamino group, butylamino group and t-butylamino group; cycloalkylamino groups such as cyclohexylamino group; phenylamino group and the like An arylamino group such as benzylamino group, and the like.

“Protection of a hydroxyl group that may be protected with a protecting group in R ^e , R ^f , R ^g , and R ^h , a mercapto group that may be protected with a protecting group, and a carboxyl group that may be protected with a protecting group Examples of the “group” include the same groups as those described as the protecting group for the hydroxyl group, mercapto group, and carboxyl group in the above-mentioned R ^a , R ^b , R ^c and R ^d .

Specific examples of the compound represented by the formula (4) include, for example, a polyamine derivative represented by the following formula (8), and R ^e , R ^f , R ^g , and R ^h are protected with a protecting group. And a compound that is a carboxyl group (for example, 1,2,4,5-benzenetetracarboxylic acid or a derivative thereof). These compounds can be used alone or in combination of two or more.

In the insulating film forming material of the present invention, preferably, the compound B is composed of a polyamine derivative represented by the formula (8). The monocyclic or polycyclic aromatic or non-aromatic ring in the ring Z ¹ of the formula (8) is the same as the monocyclic or polycyclic aromatic or non-aromatic ring in the ring Z ^b . R ⁵ , R ⁶ , R ⁷ , R ^8, an amino group which may be protected with a protecting group, a hydroxyl group which may be protected with a protecting group, and a mercapto group which may be protected with a protecting group are R It is the same as the amino group which may be protected with a protecting group in ^{e, the} hydroxyl group which may be protected with a protecting group, and the mercapto group which may be protected with a protecting group. In the formula (8), at least two of R ⁵ , R ⁶ , R ⁷ and R ⁸ are amino groups which may be protected with a protecting group. In the present invention, for example, when at least R ⁶ and R ⁷ are amino groups which may be protected with a protecting group, R ⁵ and R ⁶ , R ⁷ and R ⁸ are represented by the formula (1), ( 2) or (3) reacting with any of R ^{a to} R ^d [R ^{1 to} R ⁴ ] of adamantanepolycarboxylic acid represented by [Formula (5), (6), or (7)] to form a ring is preferably in the formable positions, in particular, so as to form a 5- or 6-membered ring, ring 1,2-position of Z ^a constituent atoms of (alpha-position) or 1,3-positions of the (beta-position) It is preferred that it is bonded to a position.

As the polyamine derivative represented by the formula (8), (i) R ⁵ , R ⁶ , R ⁷ and R ⁸ , all of the amino groups which may be protected with a protecting group are all protected with a protecting group. A compound having no amino group, (ii) a compound in which at least one of R ⁵ , R ⁶ , R ⁷ and R ⁸ is an amino group protected with an alkylidene group (ie, an imine derivative), (iii) R ⁵ , R ⁶ , a compound in which at least one of R ⁷ and R ⁸ is an acylamino group (ie, an amide derivative), (iv) at least one of R ⁵ , R ⁶ , R ⁷ and R ⁸ is an alkoxycarbonyl group or an aralkyloxycarbonyl group Examples include compounds that are protected amino groups (ie, carbamate derivatives), (v) compounds in which at least one of R ⁵ , R ⁶ , R ⁷ , and R ⁸ is a mono-substituted amino group.

As typical compounds of the polyamine derivatives exemplified in the above (i) to (v), the ring Z ¹ is limited to a benzene ring, and the number of protecting groups in the case of having a protecting group is also 4-substituted or Although the compound limited to 2 substitution body is illustrated below, it is not restricted to these. That is, when ring Z ¹ is a biphenyl ring or the like, compounds corresponding to the following compounds are exemplified.

As a typical example of a compound in which the amino group which may be protected with a protecting group among (i) R ⁵ , R ⁶ , R ⁷ and R ⁸ is an amino group which is not protected with a protecting group, 1,2,4,5-tetraaminobenzene, 1,4-diamino-2,5-dihydroxybenzene, 1,5-diamino-2,4-dihydroxybenzene, 1,4-diamino-2,5-dimercapto Examples include benzene and 1,5-diamino-2,4-dimercaptobenzene.

As a representative example of the compound (ii) in which at least one of R ⁵ , R ⁶ , R ⁷ and R ⁸ is an amino group protected with an alkylidene group (ie, an imine derivative), a compound represented by the following formula Etc.

In the imine derivative, R ⁵ and R ⁶ in formula (8) are both amino groups protected with an alkylidene group, and N, N ″ -diisopropylidene-1,2,4,5-benzenetetraamine N, N ′ ″-diisopropylidene-1,2,4,5-benzenetetraamine, N, N ″ -dicyclohexylidene-1,2,4,5-benzenetetraamine, N, N ′ "" -Dicyclohexylidene-1,2,4,5-benzenetetraamine, N, N "-dibenzylidene-1,2,4,5-benzenetetraamine, N, N""-dibenzylidene- An imine derivative in which R ⁷ and R ⁸ are both amino groups, such as 1,2,4,5-benzenetetraamine; N, N ′, N ″, N ′ ″-tetraisopropylidene-1,2,4 5-benzenetetraamine, N, N ′, N ″, N ′ ″ -Tetracyclohexylidene-1,2,4,5-benzenetetraamine, N, N ′, N ″, N ″ ″-tetrabenzylidene-1,2,4,5-benzenetetraamine, etc. Examples include imine derivatives in which R ⁷ and R ⁸ are both amino groups protected with an alkylidene group.

Further, in the imine derivative, R ⁵ and R ⁶ in the formula (8) are both amino groups protected with an alkylidene group, and N, N ″ -diisopropylidene-N ′, N ′ ″-dimethyl -1,2,4,5-benzenetetraamine, N, N ″ ″-diisopropylidene-N ′, N ″ -dimethyl-1,2,4,5-benzenetetraamine, N, N ″ -di Cyclohexylidene-N ′, N ″ ″-dimethyl-1,2,4,5-benzenetetraamine, N, N ″ ″-dicyclohexylidene-N ′, N ″ ″-dimethyl-1, 2,4,5-benzenetetraamine, N, N "-dibenzylidene-N ', N""-dimethyl-1,2,4,5-benzenetetraamine, N, N""-dibenzylidene- N ', N "'-dimethyl-1,2,4,5-benzenetetra N, N "-diisopropylidene-N ', N""-diphenyl-1,2,4,5-benzenetetraamine, N, N""-diisopropylidene-N',N"- Diphenyl-1,2,4,5-benzenetetraamine, N, N ″ -dicyclohexylidene-N ′, N ″ ′-diphenyl-1,2,4,5-benzenetetraamine, N, N ′ ″ ″ -Dicyclohexylidene-N ′, N ″ ″-diphenyl-1,2,4,5-benzenetetraamine, N, N ″ -dibenzylidene-N ′, N ″ ″-diphenyl-1, R ⁷ and R ⁸ such as 2,4,5-benzenetetraamine, N, N ″ ″-dibenzylidene-N ′, N ″ ″-diphenyl-1,2,4,5-benzenetetraamine are both Imine derivatives that are mono-substituted amino groups are included.

In addition to the above, the imine derivative includes N, N′-diisopropylidene-2,5-dihydroxy-1,4-benzenediamine, N, N′-diisopropylidene-2,4-dihydroxy-1, 5-benzenediamine, N, N'-dicyclohexylidene-2,5-dihydroxy-1,4-benzenediamine, N, N'-dicyclohexylidene-2,4-dihydroxy-1,5-benzenediamine R ⁷ and R ⁸ such as N, N′-dibenzylidene-2,5-dihydroxy-1,4-benzenediamine, N, N′-dibenzylidene-2,4-dihydroxy-1,5-benzenediamine, Imine derivatives that are both hydroxyl groups; N, N′-diisopropylidene-2,5-dimercapto-1,4-benzenediamine, N, N′-diisopropylidene-2,4 Dimercapto-1,5-benzenediamine, N, N′-dicyclohexylidene-2,5-dimercapto-1,4-benzenediamine, N, N′-dicyclohexylidene-2,4-dimercapto-1, R ⁷ such as 5-benzenediamine, N, N′-dibenzylidene-2,5-dimercapto-1,4-benzenediamine, N, N′-dibenzylidene-2,4-dimercapto-1,5-benzenediamine , And R ⁸ are both mercapto groups.

Examples of the compound (iii) in which at least one of R ⁵ , R ⁶ , R ⁷ and R ⁸ is an acylamino group (that is, an amide derivative) include compounds represented by the following formulas.

In the amide derivative, R ⁵ and R ⁶ in formula (8) are both acylamino groups, and R ⁷ and R ⁸ such as 1,2,4,5-tetrakis (acetamino) benzene are both acylamino groups. Amide derivatives: 1,4-bis (acetamino) -2,5-bis (methylamino) benzene, 1,5-bis (acetamino) -2,4-bis (methylamino) benzene, 1,4-bis (Methoxycarbonylamino) -2,5-bis (methylamino) benzene, 1,5-bis (methoxycarbonylamino) -2,4-bis (methylamino) benzene, 1,4-bis (acetamino) -2, is 5-bis (phenylamino) benzene, 1,5-bis (acetamino) -2,4-bis (phenylamino) R ^7, R ⁸ are both mono-substituted amino group, such as benzene 1,4-bis (acetamino) -2,5-diacetoxybenzene, 1,5-bis (acetamino) -2,4-diacetoxybenzene, 1,4-bis (methoxycarbonylamino) -2, Amide derivatives such as 5-dimethoxycarbonyloxybenzene, 1,5-bis (methoxycarbonylamino) -2,4-dimethoxycarbonyloxybenzene, wherein R ⁷ and R ⁸ are both hydroxyl groups protected by a protecting group; R ⁷ and R ⁸ such as 4-bis (acetamino) -2,5-diacetylthiobenzene and 1,5-bis (acetamino) -2,4-diacetylthiobenzene are both mercapto groups protected with a protecting group. Amide derivatives are included.

Examples of the compound (iv) wherein at least one of R ⁵ , R ⁶ , R ⁷ and R ⁸ is an amino group protected with an alkoxycarbonyl group or an aralkyloxycarbonyl group (that is, a carbamate derivative) Examples of the compound are represented.

In the carbamic acid ester derivative, R ⁵ and R ⁶ in formula (8) are both alkoxycarbonyl groups, and R ⁷ and R ⁸ such as 1,2,4,5-tetrakis (acetylamino) benzene are Carbamate derivatives that are both alkoxycarbonyl groups; 1,4-bis (methoxycarbonylamino) -2,5-bis (phenylamino) benzene, 1,5-bis (methoxycarbonylamino) -2,4-bis ( Phenylamino) benzene, 1,2,4,5-tetrakis (methylamino) benzene, 1,2,4,5-tetrakis (phenylamino) benzene and the like, wherein R ⁷ and R ⁸ are both mono-substituted amino groups Acid ester derivatives; 1,4-bis (methoxycarbonylamino) -2,5-dimethoxycarbonyloxybenzene, 1,5-bi Carbamic acid ester derivatives in which R ⁷ and R ⁸ are both hydroxyl groups protected by a protecting group, such as su (methoxycarbonylamino) -2,4-dimethoxycarbonyloxybenzene; 1,4-bis (methoxycarbonylamino)- Carbamate ester in which R ⁷ and R ⁸ are both mercapto groups protected by a protecting group such as 2,5-dimethoxycarbonylthiobenzene and 1,5-bis (methoxycarbonylamino) -2,4-dimethoxycarbonylthiobenzene Derivatives are included.

As a typical example of the compound (v) in which at least one of R ⁵ , R ⁶ , R ⁷ and R ⁸ is a mono-substituted amino group, R ⁵ and R ⁶ in the formula (8) are both mono-substituted amino. 1,4-diamino-2,5-bis (methylamino) benzene, 1,5-diamino-2,4-bis (methylamino) benzene, 1,4-diamino-2,5-bis Examples thereof include compounds in which R ⁷ and R ⁸ are both amino groups, such as (phenylamino) benzene and 1,5-diamino-2,4-bis (phenylamino) benzene.

In addition to the above, the polyamine derivative represented by the formula (8) includes a compound in which at least two of R ^{5 to} R ⁸ are bonded to each other to form a ring with adjacent atoms. Examples of such polyamine derivatives include compounds in which an amino group in the molecule is protected with a protecting group (polyfunctional protecting group) capable of simultaneously protecting the plurality of amino groups. As a typical example of such a compound, a compound in which 1,2,4,5-tetraaminobenzene is protected with two oxalyl groups [in the formula (8), ring Z ¹ is a benzene ring, R ⁵ and R ⁶ , R ⁷ and R ⁸ are each an amino group protected with an oxalyl group], 1,2,4,5-tetraaminobenzene protected with two butane-2,3-diylidene groups Compound [In the formula (6), ring Z is a benzene ring and R ⁵ and R ⁶ , R ⁷ and R ⁸ are each an amino group protected with a butane-2,3-diylidene group] Etc.

  These polyamine derivatives can be used alone or in combination of two or more.

  The polyamine derivative represented by the formula (8) can be obtained by a known method, a known organic synthesis reaction, a method for introducing a protecting group to a known amino group (for example, a method by acylation, iminization, alkylation, etc. ) And the like.

  The solvent in the present invention is not particularly limited as long as it dissolves compound A and compound B and does not inhibit the reaction. For example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, etc. Amides; cyclic aminoacetals such as dimethylimidazolidine; sulfoxides such as dimethyl sulfoxide; sulfones; nitriles such as acetonitrile, propionitrile, benzonitrile; acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, cyclopenta Ketones such as non and cyclohexanone; esters such as formate, acetate, propionate, benzoate, γ-butyrolactone, propylene glycol monomethyl ether acetate (PGMEA); dioxane Ethers such as tetrahydrofuran, diethyl ether, and ethylene glycol diethyl ether; Halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, and chlorobenzene; Aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and mesitylene An alicyclic hydrocarbon such as cyclohexane or methylcyclohexane; an aliphatic hydrocarbon such as hexane, heptane or octane; These solvents can be used alone or in admixture of two or more.

  The insulating film forming material of the present invention may contain components other than those described above. For example, a catalyst for promoting the polymerization reaction may be added. Typical examples of the catalyst include acid catalysts such as sulfuric acid, methanesulfonic acid, and p-toluenesulfonic acid. The usage-amount of a catalyst is 0-10 mol% with respect to the total amount of the said monomer component (Adamantane polycarboxylic acid and aromatic polyamine), Preferably it is about 0-5 mol%. Moreover, you may add the additive for adjusting the viscosity of a solution to the insulating-film formation material of this invention for the purpose of improving applicability | paintability. Typical examples of such additives include alkylene glycols and polyalkylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol, and polyethylene glycol; polybenzimidazoles; polybenzoxazoles, and the like. The amount of the additive used is, for example, 0 to 20% by weight, preferably about 0 to 10% by weight, based on the total amount of the insulating film forming material (coating liquid).

  Furthermore, monocarboxylic acids for adjusting the molecular weight after polymerization and / or dicarboxylic acids for adjusting the degree of crosslinking after polymerization may be added to the insulating film forming material of the present invention. Representative examples of monocarboxylic acids include monocarboxylic acids such as adamantane carboxylic acid and benzoic acid; monocarboxylic acid derivatives such as adamantane carboxylic acid methyl ester and benzoic acid methyl ester, and the like. Examples include dicarboxylic acids such as adamantane dicarboxylic acid and terephthalic acid; and dicarboxylic acid derivatives such as adamantane dicarboxylic acid dimethyl ester and terephthalic acid dimethyl ester. The amount of monocarboxylic acid used is, for example, about 0 to 10 mol%, preferably about 0 to 5 mol%, based on adamantane polycarboxylic acid, and the amount of dicarboxylic acid used is, for example, about adamantane polycarboxylic acid. It is 0-100 mol%, Preferably it is about 0-50 mol%.

  You may add the adhesion promoter for improving the board | substrate adhesiveness of the insulating film formed in the insulating film forming material of this invention. Typical examples of the adhesion promoter include trimethoxyvinylsilane, hexamethyldisilazane, γ-aminopropyltriethoxysilane, aluminum monoethylacetoacetate diisopropylate, and the like. The amount of the adhesion promoter used is, for example, about 0 to 10% by weight, preferably about 0 to 5% by weight, based on the total amount of the monomer components.

  The method for preparing the polymerizable composition constituting the insulating film forming material of the present invention is not particularly limited as long as it is a method capable of completely dissolving the types of the compounds A and B (monomer components) in a solvent. It is carried out by stirring or standing a mixture comprising a monomer component, a solvent and other components. The use ratio of Compound A and Compound B can be selected within a wide range, and both may be used in an equivalent amount, or either one may be used in an excess amount. In general, an excessive amount of Compound B is often used. For example, the amount of compound B used is generally 0.01 to 100 equivalents, preferably 1 to 50 equivalents, more preferably about 4 to 20 equivalents, relative to compound A.

  The concentration of the total amount of Compound A and Compound B (total monomer amount) in the solvent is arbitrarily selected according to the solubility in the solvent used, and the total monomer concentration is, for example, 5 to 70% by weight, preferably 10 to 60%. It is about wt%. An insulating film formed of an insulating film forming material in which a high concentration of monomer components is dissolved exhibits excellent electrical characteristics because the film thickness can be increased, and has an insulating film thickness suitable for various semiconductor manufacturing processes. A film can be formed. Further, the monomer component does not precipitate in the insulating film forming material, and excellent coating properties can be exhibited.

  The dissolution is performed, for example, in an air atmosphere, and preferably in an inert gas atmosphere such as nitrogen or argon, as long as the polyamine derivative as the compound B is not oxidized. The temperature for dissolving is not particularly limited, and may be heated according to the solubility of the monomer and the boiling point of the solvent, and is, for example, about 0 to 200 ° C., preferably about 10 to 150 ° C.

  The insulating film of the present invention is composed of a polymer (polymer crosslinked product) formed from the compound A and the compound B. The insulating film is formed, for example, by applying an insulating film forming material made of a polymerizable composition on a substrate and then heating to cause a polymerization reaction. Examples of the base material include a silicon wafer, a metal substrate, and a ceramic substrate. The application method is not particularly limited, and conventional methods such as spin coating, dip coating, and spraying can be used.

  The heating temperature is not particularly limited as long as the polymerizable component to be used is polymerized, but is, for example, about 100 to 500 ° C, preferably about 150 to 450 ° C, and may be given a constant temperature or a stepwise temperature gradient. The heating may be performed, for example, in an air atmosphere as long as the performance of the formed thin film is not affected, and is preferably performed in an inert gas (nitrogen, argon, etc.) atmosphere or a vacuum atmosphere.

By heating, a polymerization reaction proceeds by bonding between the functional group of compound A and the functional group of compound B contained in the insulating film forming material. For example, a carboxyl group or a haloformyl group that may be protected with a protecting group in R ¹ , R ² , R ³ , R ⁴ of the polycarboxylic acid derivative represented by the above formulas (5) to (7), and the above formula In the polyamine derivative represented by (8), an amino group which may be protected with a protecting group in R ⁵ , R ⁶ , R ⁷ and R ⁸ , a hydroxyl group which may be protected with a protecting group, or a protecting group Reaction with an optionally protected mercapto group produces a polymer in which an amide bond, ester bond or thioester bond is formed. In addition, when one or two of R ^{5 to} R ⁸ are a hydroxyl group which may be protected with a protecting group or a mercapto group which may be protected with a protecting group, an ester bond or a thioester bond is not formed. In some cases, only an amide bond is formed. As a typical example of the bond between Compound A and Compound B, adamantane polycarboxylic acids and aromatic polyamines are polycondensed with elimination of a protecting group for a carboxyl group and / or a protecting group for an amino group. As a polymerization product, adamantane skeleton-containing polybenzazoles (imidazole, oxazole, thiazoles) and the like are formed.

  In particular, in the present invention, since the compound A is a combination of a tetrafunctional compound and a trifunctional compound and / or a bifunctional compound, the distance (side) between adjacent crosslinking points (or nodal points) is long and large. Is formed, and as a result, a very low dielectric constant can be achieved. More specifically, the tetrafunctional compound constituting the compound A forms a crosslinking point having a three-dimensional structure branched in four directions, and the trifunctional compound forms a crosslinking point having a three-dimensional structure branched in three directions. The functional compound forms a nodal point having a linear two-dimensional structure extending in two directions, whereby a compound A and a compound B, which are a combination of a tetrafunctional compound and a trifunctional compound and / or a bifunctional compound, are formed. Bonding can produce a polymer with a loose pore structure. For example, when the compound A is a combination of a tetrafunctional compound and a trifunctional compound, a steric hindrance occurs with each other, so that a polymer having a large void formed by a polymerization reaction due to a bond with the compound B is obtained. Further, in the case of a combination of a tetrafunctional compound and a bifunctional compound, a cross-linking point formed by the tetrafunctional compound is used as a vertex, and a connecting portion formed by the compound B bonded to the tetrafunctional compound and a knot composed of the bifunctional compound. A large void is formed with the outer periphery of the connecting portion of compound B bonded to the point. On the other hand, the tetrafunctional compound (trifunctional compound) alone increases the density because many crosslinking points are formed during polymerization, and also reduces the degree of molecular freedom, resulting in uncrosslinked points and increasing the relative dielectric constant. If the bifunctional compound is used alone, the polymer to be formed has a chain structure and is low in volume, so that the polymers are likely to be close to each other and become a high-density insulating film. Therefore, when a combination of a tetrafunctional compound and a trifunctional compound and / or a bifunctional compound is used, the tetrafunctional compound is compared with the case where a polymer is obtained using only one of the three compounds as the compound A. A low-density sparse vacant structure having a structural part crosslinked in four directions as a crosslinking point can be formed.

  The insulating film of the present invention includes a three-dimensional structure branched in four directions formed by bonding of a tetrafunctional compound and a compound B contained in a polymer formed from the insulating film forming material, and a trifunctional compound and a compound B. It has a three-dimensional structure branched by three bonds, or a combination of a chain-like two-dimensional structure extending in two directions formed by a bond between a bifunctional compound and compound B. . As a preferred embodiment of the insulating film of the present invention, an adamantane ring, an aromatic ring, and an azole ring contained in a polymer formed from an insulating film forming material in which the central skeletons of the compounds A and B are an adamantane skeleton and an aromatic ring skeleton, respectively. Alternatively, it contains a 6-membered nitrogen-containing ring (ring formed in the polycondensation moiety) as the main structural unit. In such an insulating film, for example, by using adamantanetricarboxylic acid as a trifunctional compound, an adamantane compound having a three-dimensional structure and an aromatic polyamine having a two-dimensional structure are combined to form an apex (crosslinking point). ), A polymer film having a structure cross-linked in three directions (a unit in which three hexagons share two vertices or two sides with each other) is formed. In addition, by using adamantanetetracarboxylic acid as a tetrafunctional compound, a network having a structure (units in which three hexagons share two sides) with the adamantane skeleton as a vertex (crosslinking point) in four directions is used. The polymer film can be formed. Since such an insulating film has a large number of molecular-level holes uniformly dispersed therein, it can have a particularly excellent relative dielectric constant.

  The thickness of the insulating film formed by heating can be appropriately set depending on the application, but is generally 50 nm or more (about 50 to 2000 nm), preferably 100 nm or more (about 100 to 2000 nm), more preferably 300 nm or more (300 About 2000 nm). According to the insulation forming material of the present invention, since a coating solution having a high monomer concentration can be obtained, the above film thickness can be realized even with an insulation film made of polybenzazoles. If the thickness is less than 50 nm, the electrical characteristics such as leakage current are adversely affected, and problems such as difficulty in planarizing the film by chemical mechanical polishing (CMP) in the semiconductor manufacturing process are likely to occur. Not suitable for insulating film applications.

  In addition, it is conceivable to form an insulating film by applying a pre-manufactured polymer (polymer cross-linked product) on the substrate, but since such a polymer has extremely low solubility in a solvent, a thin film is formed by coating It is difficult to do. On the other hand, the insulating film forming material of the present invention can easily dissolve the monomer component in the solvent and prepare a solution having a high concentration. A thin film having a thickness can be easily formed. The insulating film made of the polymer thus formed has the advantage that the voids are large and the porosity is extremely high, so that the relative dielectric constant is extremely low, and the bridge has sufficient heat resistance and mechanical strength. Have.

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

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. The film thickness of the polymer film was measured using an ellipsometer. The density of the polymer film was determined by analysis of X-ray reflectivity measurement, and the relative dielectric constant of the polymer film was measured by forming an Al electrode on the surface of the film. Infrared absorption spectrum was measured using a thin film transmission method. “S”, “m”, and “w” in infrared absorption spectrum data indicate “strong” absorption, “medium” absorption, and “weak” absorption, respectively.

Example 1
In a three-necked flask, 2.92 g (13.6 mmol) of 3,3′-diaminobenzidine and 100 ml of cyclohexanone were added and dissolved, followed by stirring at 40 ° C. for 40 minutes in a nitrogen stream to obtain liquid A. In a separate flask, 1.50 g (11.2 mmol) of 1,3-adamantane dicarboxylic acid and 0.39 g (1.2 mmol) of 1,3,5,7-adamantanetetracarboxylic acid were dissolved in 18 g of DMAc. A liquid [bifunctional compound: tetrafunctional compound (molar ratio) = 90: 10] was obtained. Liquid B was added to the flask of liquid A and stirred at room temperature for 10 minutes to prepare a coating solution having a monomer concentration of 4.7% by weight.
This coating solution was passed through a filter having a pore diameter of 0.1 micron, and then spin-coated on an 8-inch silicon wafer. This was heated from 300 ° C. to 300 ° C. in a nitrogen atmosphere and held for 30 minutes, then heated to 400 ° C. over 20 minutes and held for another 30 minutes, and then cooled to form a film. When the infrared absorption spectrum of the polymer film thus obtained was measured, the following infrared absorption spectrum data was obtained, and it was confirmed that the desired crosslinked polybenzimidazole film was formed. The film thickness of the obtained film was 210 nm. The density of the film was 1.22 g / ml and the relative dielectric constant was 2.4.
Infrared absorption spectrum data (cm ⁻¹ ):
806, 1282, 1333, 1403, 1450, 1520, 1626, 2860, 2910, 3412

Example 2
In a three-necked flask, 3.03 g (14.1 mmol) of 3,3′-diaminobenzidine and 100 ml of cyclohexanone were added and dissolved, and the mixture was stirred at 40 ° C. for 40 minutes in a nitrogen stream to obtain liquid A. In a separate flask, 1.90 g (8.5 mmol) of 1,3-adamantane dicarboxylic acid and 0.88 g (2.8 mmol) of 1,3,5,7-adamantanetetracarboxylic acid were dissolved in 18 g of DMAc. A liquid [bifunctional compound: tetrafunctional compound (molar ratio) = 75: 25] was obtained. Liquid B was added to the flask of liquid A and stirred at room temperature for 10 minutes to prepare a coating solution having a monomer concentration of 4.7% by weight.
This coating solution was passed through a filter having a pore diameter of 0.1 micron, and then spin-coated on an 8-inch silicon wafer. This was heated from 300 ° C. to 300 ° C. in a nitrogen atmosphere and held for 30 minutes, then heated to 400 ° C. over 20 minutes and held for another 30 minutes, and then cooled to form a film. When the infrared absorption spectrum of the polymer film thus obtained was measured, the same spectrum data as in Example 1 was obtained, and it was confirmed that the target crosslinked polybenzimidazole film was formed. The film thickness obtained was 195 nm. The density of the film was 1.23 g / ml, and the relative dielectric constant was 2.5.

Example 3
In a three-necked flask, 3.06 g (14.3 mmol) of 3,3′-diaminobenzidine and 100 ml of cyclohexanone were dissolved and stirred under a nitrogen stream at 40 ° C. for 40 minutes to obtain a liquid A. In a separate flask, 1.20 g (5.4 mmol) of 1,3-adamantane dicarboxylic acid and 1.39 g (4.5 mmol) of 1,3,5,7-adamantanetetracarboxylic acid were dissolved in 18 g of DMAc. A liquid [bifunctional compound: tetrafunctional compound (molar ratio) = 50: 50] was obtained. Liquid B was added to the flask of liquid A and stirred for 10 minutes at room temperature to prepare a coating solution having a monomer concentration of 4.6% by weight.
This coating solution was passed through a filter having a pore diameter of 0.1 micron, and then spin-coated on an 8-inch silicon wafer. This was heated from 300 ° C. to 300 ° C. in a nitrogen atmosphere and held for 30 minutes, then heated to 400 ° C. over 20 minutes and held for another 30 minutes, and then cooled to form a film. When the infrared absorption spectrum of the polymer film thus obtained was measured, the same spectrum data as in Example 1 was obtained, and it was confirmed that the target crosslinked polybenzimidazole film was formed. The film thickness of the obtained film was 208 nm. The density of the film was 1.24 g / ml and the relative dielectric constant was 2.6.

Example 4
In a three-necked flask, 3.21 g (15.0 mmol) of 3,3′-diaminobenzidine and 100 ml of cyclohexanone were dissolved and stirred under a nitrogen stream at 40 ° C. for 40 minutes to obtain liquid A. In a separate flask, 0.48 g (2.1 mmol) of 1,3-adamantane dicarboxylic acid and 2.01 g (6.4 mmol) of 1,3,5,7-adamantanetetracarboxylic acid were dissolved in 18 g of DMAc, and B A liquid [bifunctional compound: tetrafunctional compound (molar ratio) = 25: 75] was obtained. Liquid B was added to the flask of liquid A and stirred for 10 minutes at room temperature to prepare a coating solution having a monomer concentration of 4.6% by weight.
This coating solution was passed through a filter having a pore diameter of 0.1 micron, and then spin-coated on an 8-inch silicon wafer. This was heated from 300 ° C. to 300 ° C. in a nitrogen atmosphere and held for 30 minutes, then heated to 400 ° C. over 20 minutes and held for another 30 minutes, and then cooled to form a film. When the infrared absorption spectrum of the polymer film thus obtained was measured, the same spectrum data as in Example 1 was obtained, and it was confirmed that the target crosslinked polybenzimidazole film was formed. The film thickness of the obtained film was 208 nm. The density of the film was 1.26 g / ml, and the relative dielectric constant was 2.7.

Example 5
In a three-necked flask, 3.19 g (14.9 mmol) of 3,3′-diaminobenzidine and 100 ml of cyclohexanone were added and dissolved, followed by stirring at 40 ° C. for 40 minutes under a nitrogen stream to obtain a liquid A. In a separate flask, 0.18 g (0.7 mmol) of 1,3-adamantane dicarboxylic acid and 2.20 g (7.1 mmol) of 1,3,5,7-adamantanetetracarboxylic acid were dissolved in 18 g of DMAc. A liquid [bifunctional compound: tetrafunctional compound (molar ratio) = 10: 90] was obtained. Liquid B was added to the flask of liquid A and stirred at room temperature for 10 minutes to prepare a coating liquid having a monomer concentration of 4.5% by weight.
This coating solution was passed through a filter having a pore diameter of 0.1 micron, and then spin-coated on an 8-inch silicon wafer. This was heated from 300 ° C. to 300 ° C. in a nitrogen atmosphere and held for 30 minutes, then heated to 400 ° C. over 20 minutes and held for another 30 minutes, and then cooled to form a film. When the infrared absorption spectrum of the polymer film thus obtained was measured, the same spectrum data as in Example 1 was obtained, and it was confirmed that the target crosslinked polybenzimidazole film was formed. The film thickness of the obtained film was 208 nm. The density of the film was 1.29 g / ml, and the relative dielectric constant was 2.8.

Example 6
In a three-necked flask, 2.96 g (13.6 mmol) of 3,3′-dihydroxybenzidine and 100 ml of cyclohexanone were dissolved and stirred under a nitrogen stream at 40 ° C. for 40 minutes to obtain liquid A. In a separate flask, 1.50 g (11.2 mmol) of 1,3-adamantane dicarboxylic acid and 0.39 g (1.2 mmol) of 1,3,5,7-adamantanetetracarboxylic acid were dissolved in 18 g of DMAc. A liquid [bifunctional compound: tetrafunctional compound (molar ratio) = 90: 10] was obtained. Liquid B was added to the flask of liquid A and stirred at room temperature for 10 minutes to prepare a coating solution having a monomer concentration of 4.7% by weight.
This coating solution was passed through a filter having a pore diameter of 0.1 micron, and then spin-coated on an 8-inch silicon wafer. This was heated from 300 ° C. to 300 ° C. in a nitrogen atmosphere and held for 30 minutes, then heated to 400 ° C. over 20 minutes and held for another 30 minutes, and then cooled to form a film. When the infrared absorption spectrum of the polymer film thus obtained was measured, the same spectrum data as in Example 1 was obtained, and it was confirmed that the target crosslinked polybenzimidazole film was formed. The film thickness of the obtained film was 210 nm. The density of the film was 1.22 g / ml and the relative dielectric constant was 2.4.

Example 7
In a three-necked flask, 3.07 g (14.1 mmol) of 3,3′-dihydroxybenzidine and 100 ml of cyclohexanone were added and dissolved, and stirred at 40 ° C. for 40 minutes in a nitrogen stream to obtain liquid A. In a separate flask, 1.90 g (8.5 mmol) of 1,3-adamantane dicarboxylic acid and 0.88 g (2.8 mmol) of 1,3,5,7-adamantanetetracarboxylic acid were dissolved in 18 g of DMAc. A liquid [bifunctional compound: tetrafunctional compound (molar ratio) = 75: 25] was obtained. Liquid B was added to the flask of liquid A and stirred at room temperature for 10 minutes to prepare a coating solution having a monomer concentration of 4.7% by weight.
This coating solution was passed through a filter having a pore diameter of 0.1 micron, and then spin-coated on an 8-inch silicon wafer. This was heated from 300 ° C. to 300 ° C. in a nitrogen atmosphere and held for 30 minutes, then heated to 400 ° C. over 20 minutes and held for another 30 minutes, and then cooled to form a film. When the infrared absorption spectrum of the polymer film thus obtained was measured, the same spectrum data as in Example 1 was obtained, and it was confirmed that the target crosslinked polybenzimidazole film was formed. The film thickness obtained was 195 nm. The density of the film was 1.23 g / ml, and the relative dielectric constant was 2.5.

Example 8
In a three-necked flask, 3.10 g (14.3 mmol) of 3,3′-dihydroxybenzidine and 100 ml of cyclohexanone were dissolved and stirred under a nitrogen stream at 40 ° C. for 40 minutes to obtain liquid A. In a separate flask, 1.20 g (5.4 mmol) of 1,3-adamantane dicarboxylic acid and 1.39 g (4.5 mmol) of 1,3,5,7-adamantanetetracarboxylic acid were dissolved in 18 g of DMAc. A liquid [bifunctional compound: tetrafunctional compound (molar ratio) = 50: 50] was obtained. Liquid B was added to the flask of liquid A and stirred for 10 minutes at room temperature to prepare a coating solution having a monomer concentration of 4.6% by weight.
This coating solution was passed through a filter having a pore diameter of 0.1 micron, and then spin-coated on an 8-inch silicon wafer. This was heated from 300 ° C. to 300 ° C. in a nitrogen atmosphere and held for 30 minutes, then heated to 400 ° C. over 20 minutes and held for another 30 minutes, and then cooled to form a film. When the infrared absorption spectrum of the polymer film thus obtained was measured, the same spectrum data as in Example 1 was obtained, and it was confirmed that the target crosslinked polybenzimidazole film was formed. The film thickness of the obtained film was 208 nm. The density of the film was 1.24 g / ml and the relative dielectric constant was 2.6.

Example 9
In a three-necked flask, 3.26 g (15.0 mmol) of 3,3′-dihydroxybenzidine and 100 ml of cyclohexanone were dissolved and stirred under a nitrogen stream at 40 ° C. for 40 minutes to obtain liquid A. In a separate flask, 0.48 g (2.1 mmol) of 1,3-adamantane dicarboxylic acid and 2.01 g (6.4 mmol) of 1,3,5,7-adamantanetetracarboxylic acid were dissolved in 18 g of DMAc, and B A liquid [bifunctional compound: tetrafunctional compound (molar ratio) = 25: 75] was obtained. Liquid B was added to the flask of liquid A and stirred for 10 minutes at room temperature to prepare a coating solution having a monomer concentration of 4.6% by weight.
This coating solution was passed through a filter having a pore diameter of 0.1 micron, and then spin-coated on an 8-inch silicon wafer. This was heated from 300 ° C. to 300 ° C. in a nitrogen atmosphere and held for 30 minutes, then heated to 400 ° C. over 20 minutes and held for another 30 minutes, and then cooled to form a film. When the infrared absorption spectrum of the polymer film thus obtained was measured, the same spectrum data as in Example 1 was obtained, and it was confirmed that the target crosslinked polybenzimidazole film was formed. The film thickness of the obtained film was 208 nm. The density of the film was 1.26 g / cm ³ and the relative dielectric constant was 2.7.

Example 10
In a three-necked flask, 3.23 g (14.9 mmol) of 3,3′-dihydroxybenzidine and 100 ml of cyclohexanone were dissolved and stirred under a nitrogen stream at 40 ° C. for 40 minutes to obtain liquid A. In a separate flask, 0.18 g (0.7 mmol) of 1,3-adamantane dicarboxylic acid and 2.20 g (7.1 mmol) of 1,3,5,7-adamantanetetracarboxylic acid were dissolved in 18 g of DMAc. A liquid [bifunctional compound: tetrafunctional compound (molar ratio) = 10: 90] was obtained. Liquid B was added to the flask of liquid A and stirred at room temperature for 10 minutes to prepare a coating liquid having a monomer concentration of 4.5% by weight.
This coating solution was passed through a filter having a pore diameter of 0.1 micron, and then spin-coated on an 8-inch silicon wafer. This was heated from 300 ° C. to 300 ° C. in a nitrogen atmosphere and held for 30 minutes, then heated to 400 ° C. over 20 minutes and held for another 30 minutes, and then cooled to form a film. When the infrared absorption spectrum of the polymer film thus obtained was measured, the same spectrum data as in Example 1 was obtained, and it was confirmed that the target crosslinked polybenzimidazole film was formed. The film thickness of the obtained film was 208 nm. The density of the film was 1.29 g / ml, and the relative dielectric constant was 2.8.

Comparative Example 1
In Example 1, 3.19 g (14.9 mmol) of 3,3′-diaminobenzidine was used, and 2.50 g of 1,3-adamantane dicarboxylic acid and 0.39 g of 1,3,5,7-adamantane tetracarboxylic acid were used. The same procedure as in Example 1 was carried out except that 2.35 g (7.48 mmol) of 1,3,5,7-adamantanetetracarboxylic acid was used instead of the combination of A coating solution was prepared.
This coating solution was passed through a filter having a pore diameter of 0.1 micron, and then spin-coated on an 8-inch silicon wafer. This was heated from 300 ° C. to 300 ° C. in a nitrogen atmosphere and held for 30 minutes, then heated to 400 ° C. over 20 minutes and held for another 30 minutes, and then cooled to form a film. When the infrared absorption spectrum of the polymer film thus obtained was measured, the following infrared absorption spectrum data was obtained, and it was confirmed that the desired crosslinked polybenzimidazole film was formed. The film thickness of the obtained film was 210 nm. The density of the film was 1.22 g / ml and the relative dielectric constant was 3.0.

Claims (3)

Each compound has two or more functional groups or functional group groups in the molecule, and is polymerized by bonding between the functional group or functional group group of one compound and the functional group or functional group group of the other compound. An insulating film forming material comprising a polymerizable composition obtained by dissolving two compounds A and B capable of forming a polymer having a pore structure in a solvent, wherein the compound A is a tetrafunctional compound and It is a combination with a trifunctional compound and / or a bifunctional compound, and the tetrafunctional compound, trifunctional compound, and bifunctional compound in Compound A are each a tetracarboxylic acid derivative represented by the following formula (5), the following formula ( 6) and a dicarboxylic acid derivative represented by the following formula (7)

(In the formula, Z ^a represents a tetravalent adamantyl group, R ¹ , R ² , R ³ and R ⁴ are the same or different and each represents a carboxyl group or a haloformyl group which may be protected with a protective group; Y ¹ , Y ² , Y ³ , Y ⁴ are the same or different and each represents a single bond or a divalent aromatic or non-aromatic cyclic group, and L ¹ and L ³ are the same or different, Represents a hydrogen atom or a hydrocarbon group)
[Tetrafunctional compound] / [trifunctional compound and / or bifunctional compound] (molar ratio) is 10/90 to 90/10, and compound B is represented by the following formula (8):

(In the formula, ring Z ¹ represents a monocyclic or polycyclic aromatic or non-aromatic ring, and R ⁵ , R ⁶ , R ⁷ and R ⁸ are substituents bonded to ring Z ^1. And an amino group which may be protected with a protecting group, a hydroxyl group which may be protected with a protecting group, or a mercapto group which may be protected with a protecting group, provided that R ⁵ is the same or different. , R ⁶ , R ⁷ and R ⁸ are amino groups optionally protected by a protecting group)
An insulating film forming material which is a polyamine derivative represented by: Each compound has two or more functional groups or functional group groups in the molecule, and is polymerized by bonding between the functional group or functional group group of one compound and the functional group or functional group group of the other compound. A polymer obtained by a polymerization reaction between two compounds A and B capable of forming a polymer having a pore structure, wherein the compound A is a tetrafunctional compound, a trifunctional compound, and / or a bifunctional compound, and A tetrafunctional compound in compound A, a trifunctional compound, and a bifunctional compound, respectively, a tetracarboxylic acid derivative represented by the following formula (5), a tricarboxylic acid derivative represented by the following formula (6), And a dicarboxylic acid derivative represented by the following formula (7):

(Where Z ^a Represents a tetravalent adamantyl group, R ¹ , R ² , R ^Three , R ^Four Are the same or different and each represents a carboxyl group or a haloformyl group which may be protected with a protecting group; ¹ , Y ² , Y ^Three , Y ^Four Are the same or different and each represents a single bond or a divalent aromatic or non-aromatic cyclic group; ¹ , L ^Three Are the same or different and each represents a hydrogen atom or a hydrocarbon group)
[Tetrafunctional compound] / [trifunctional compound and / or bifunctional compound] (molar ratio) is 10/90 to 90/10, and compound B is represented by the following formula (8):

(Wherein ring Z ¹ Represents a monocyclic or polycyclic aromatic or non-aromatic ring, R ^Five , R ⁶ , R ⁷ , R ⁸ Is ring Z ¹ The same or different, and may be protected with an amino group which may be protected with a protecting group, a hydroxyl group which may be protected with a protecting group, or a protecting group. Represents a mercapto group; However, R ^Five , R ⁶ , R ⁷ , R ⁸ At least two of them are amino groups optionally protected by a protecting group)
A polymer which is a polyamine derivative represented by: An insulating film made of the polymer according to claim 2.