JP2003292878A - Coating liquid for forming insulating film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coating liquid for forming an insulating film which can form an insulating film having a low relative dielectric constant and exhibiting excellent insulating performances. <P>SOLUTION: The coating liquid for forming an insulating film comprises at least one selected from the group consisting of a compound represented by formula (1) and a resin obtained by polymerizing the compound represented by formula (1). The method for forming an insulating film comprises applying the coating liquid on a substrate and effecting a heat treatment. The method for forming an insulating film comprises applying the coating liquid on a substrate and effecting a heat treatment thereby causing three-dimensional crosslinking. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a coating liquid for forming an insulating film.

[0002]

2. Description of the Related Art In recent years, with the miniaturization of wiring in semiconductor devices, there has been a problem of so-called wiring delay in which the transmission speed of electronic signals becomes slow. In order to solve the problem of wiring delay, measures such as improving the performance of the wiring itself and reducing the interference between the wirings can be given. As a method for reducing the interference between wirings, there is a performance improvement of the insulating film. In order to improve the performance of the insulating film, development of an insulating film having a lower relative dielectric constant is desired.

Since the relative permittivity is known to be proportional to the electronic polarizability, an organic material having a low electronic polarizability is drawing attention. A benzocyclobutene-based polymer is known as an organic material having a low electronic polarizability, but the relative dielectric constant of the polymer is 2.6 (see Non-Patent Document 1), and the insulating performance is not sufficient. There wasn't. Therefore, it has been desired to develop a coating liquid that can form an insulating film having excellent insulating performance.

[0004]

[Non-Patent Document 1] Fine Chemicals, Vol.28 (No.14),
p16, (1999)

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a coating liquid for forming an insulating film, which can form an insulating film having a low relative permittivity and an excellent insulating performance.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies in order to find a coating liquid for forming an insulating film that can solve the above problems, and as a result, polymerized adamantane derivatives and adamantane derivatives. The inventors have found that a coating liquid containing at least one selected from the group consisting of the obtained resins can form an insulating film having a low relative dielectric constant, and completed the present invention.

That is, the present invention is characterized by containing at least one selected from the group consisting of a compound represented by the formula (1) and a resin obtained by polymerizing the compound represented by the formula (1). The present invention provides a coating liquid for forming an insulating film. (1) (In the formula, X ¹ is an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a monovalent organic group represented by formula (2), or represented by formula (3). Represents a monovalent organic group,
They may be the same or different from each other, and X ² represents a hydrogen atom or a halogen atom, a hydroxyl group, or a carbon number of 1 to 6
Represents an alkyl group, an alkyloxy group having 1 to 6 carbon atoms, a phenoxy group, or an aryl group which may be substituted, and when there are a plurality of groups, they may be the same or different from each other,
n represents an integer of 2 to 16 and m = 16-n. ) —Y ¹ —Ar ¹ (2) (In the formula, Y ¹ represents an alkenylene group having 2 to 6 carbon atoms or an alkynylene group having 2 to 6 carbon atoms, and Ar ¹ represents an aryl group which may be substituted. ^{represents) -Y 2 -Ar 2 -. (} Y 3 -A) p (3) ( wherein, Y ² is a direct bond, an alkylene group having 1 to 6 carbon atoms, an alkenylene group having 2 to 6 carbon atoms or, 2 to 2 carbon atoms
6 represents an alkynylene group, Y ³ represents an alkylene group having 1 to 6 carbon atoms, an alkenylene group having 2 to 6 carbon atoms, or an alkynylene group having 2 to 6 carbon atoms, and either Y ² or Y ³ is present. Alkenylene group having 2 to 6 carbon atoms or 2 carbon atoms
To 6 are alkynylene groups, p is an integer of 1 to 5, Ar ² represents an optionally substituted arylene group, and A represents a hydrogen atom or an optionally substituted aryl group. , P is 2 or more, Y ³ and A may be the same or different. )

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The coating liquid for forming an insulating film of the present invention is
It contains at least one selected from the group consisting of the compound represented by the above formula (1) and a resin obtained by polymerizing the compound represented by the formula (1). Here, X ¹ is an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a monovalent organic group represented by the above formula (2), or a monovalent group represented by the above formula (3). Represents an organic group, and may be the same or different from each other. X ¹ is preferably an alkynyl group having 2 to 6 carbon atoms, a monovalent organic group represented by the formula (2) or a monovalent organic group represented by the formula (3).
Examples of the alkenyl group having 2 to 6 carbon atoms include vinyl group, allyl group, propenyl group, butenyl group, butazinyl group and hexenyl group, and the position of double bond is not particularly limited. Examples of the alkynyl group having 2 to 6 carbon atoms include an ethynyl group, a propynyl group, a butynyl group and a hexynyl group, and the position of the triple bond is not particularly limited.

Examples of Y ¹ of the monovalent organic group represented by the formula (2) include alkenylene groups having 2 to 6 carbon atoms such as vinylene group, propenylene group and butenylene group, or ethynylene group, propynylene group, butynylene group. Group, an alkynylene group having 2 to 6 carbon atoms such as a butadinylene group.

Ar ¹ represents an optionally substituted aryl group, and specific examples thereof include a phenyl group, a methylphenyl group, a dimethylphenyl group, an ethylphenyl group, a diethylphenyl group, a trimethylphenyl group and a tetramethylphenyl group. , Pentamethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, fluorophenyl group, chlorophenyl group, bromophenyl group, iodophenyl group, nitrophenyl group, cyanophenyl group, carboxyphenyl group,
Methyloxycarbonylphenyl group, aminophenyl group, naphthyl group, methylnaphthyl group, dimethylnaphthyl group, ethylnaphthyl group, diethylnaphthyl group, trimethylnaphthyl group, tetramethylnaphthyl group, pentamethylnaphthyl group, hydroxynaphthyl group, methoxynaphthyl group , Ethoxynaphthyl group, phenoxynaphthyl group, fluoronaphthyl group, chloronaphthyl group, bromonaphthyl group, iodonaphthyl group, nitronaphthyl group, cyanonaphthyl group, carboxynaphthyl group, methyloxycarbonylnaphthyl group, aminonaphthyl group, biphenyl group, Examples thereof include anthracenyl group.

Y ² of the monovalent organic group represented by the formula (3) is
Direct bond, alkylene group having 1 to 6 carbon atoms, 2 to 6 carbon atoms
Or an alkynylene group having 2 to 6 carbon atoms. Examples of the alkylene group having 1 to 6 carbon atoms include methylene group, ethylene group, propylene group and hexylene group. Examples of the alkenylene group having 2 to 6 carbon atoms and the alkynylene group having 2 to 6 carbon atoms include the same groups as described above.

Y ³ represents an alkenyl group having 2 to 6 carbon atoms or an alkynyl group having 2 to 6 carbon atoms. p represents an integer of 1 to 5, and p is preferably 1 or 2. Examples of the alkenyl group having 2 to 6 carbon atoms and the alkynyl group having 2 to 6 carbon atoms include the same groups as described above.

Ar ² represents an optionally substituted arylene group, and specific examples thereof include a phenylene group, a methylphenylene group, a dimethylphenylene group, an ethylphenylene group, a diethylphenylene group, a trimethylphenylene group,
Alkylphenylene groups such as tetramethylphenylene group, pentamethylphenylene group, methoxyphenylene group,
An alkoxyphenylene group such as an ethoxyphenylene group,
Fluorophenylene group, chlorophenylene group, bromophenylene group, halophenylene group such as iodophenylene group, methylnaphthylene group, dimethylnaphthylene group, ethylnaphthylene group, diethylnaphthylene group, trimethylnaphthylene group, tetramethylnaphthylene group, Alkylnaphthylene group such as pentamethylnaphthylene group, alkoxynaphthylene group such as methoxynaphthylene group, ethoxynaphthylene group, fluoronaphthylene group, halonaphthylene group such as chloronaphthylene group, bromonaphthylene group, halonaphthylene group such as iodonaphthylene group, hydroxyphenylene group Group, phenoxyphenylene group, nitrophenylene group, cyanophenylene group, carboxyphenylene group, methyloxycarbonylphenylene group, aminophenylene group, naphthylene group, hydroxynaphthylene group Group, phenoxy Sina border alkylene group, Nitoronafuchiren group, Shianonafuchiren group, carboxyanhydride Sina border alkylene group, methyloxycarbonyl naphthylene group, Aminonafuchiren group, biphenylene group, etc. Antoraseren group.

A represents a hydrogen atom or an optionally substituted aryl group. Examples of the aryl group which may be substituted include the same ones as described above.

Since X ¹ has high reactivity during polymerization,
It is preferable to include a carbon-carbon triple bond. X ¹ is an alkynyl group having 2 to 6 carbon atoms, Y ¹ is an alkynylene group having 2 to 6 carbon atoms, and the monovalent organic group represented by the formula (2) or Y ² or Y ³ has 2 carbon atoms. It is preferably a monovalent organic group represented by the formula (3), which is an alkynylene group represented by any of the formulas 1 to 6.

More preferably, X ¹ is a monovalent organic group selected from the following group. In the formula, Ar ¹ , Ar ² , A and p have the same meanings as described above. When X ¹ is a monovalent organic group selected from the following group, alkynylene groups react with each other, and the chemical structure is an aromatic ring,
Since it has a polyvinylene skeleton or a polyacetylene skeleton, the mechanical strength of the obtained insulating film is increased, which is more preferable.

X ¹ is more preferably a monovalent organic group selected from the following group, because an insulating film having a low polarizability and a low relative dielectric constant can be obtained. In the formula, q, r, s, and t each independently represent an integer of 0 to 5, q + r is 1 to 5 and s + t is 0 to 5 or less.

X ¹ is particularly preferably a monovalent organic group selected from the following group. A monovalent organic group selected from the following group is particularly preferable because the raw materials acetylene, ethynylbenzene, diphenylacetylene, and ethynyldiphenylacetylene are easily available.

X ² represents a hydrogen atom or a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, or 1 carbon atom.
Represents an alkyloxy group, a phenoxy group, or an optionally substituted aryl group of 6 to 6, and may be the same or different from each other. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Carbon number 1
Examples of the alkyl group of to 6 include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group and the like. Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group and a hexoxy group. Examples of the optionally substituted aryl group include, for example, a methylphenyl group, a dimethylphenyl group, an ethylphenyl group, a diethylphenyl group,
Alkylphenyl groups such as trimethylphenyl group, tetramethylphenyl group, pentamethylphenyl group, alkoxyphenyl groups such as methoxyphenyl group, ethoxyphenyl group, fluorophenyl group, chlorophenyl group, bromophenyl group, alkoxyphenyl such as iodophenyl group Group, methylnaphthyl group, dimethylnaphthyl group, ethylnaphthyl group, diethylnaphthyl group, trimethylnaphthyl group, tetramethylnaphthyl group, alkylnaphthyl group such as pentamethylnaphthyl group, methoxynaphthyl group,
Alkoxynaphthyl group such as ethoxynaphthyl group, fluoronaphthyl group, chloronaphthyl group, halonaphthyl group such as bromonaphthyl group, iodonaphthyl group, phenyl group, hydroxyphenyl group, phenoxyphenyl group, nitrophenyl group, cyanophenyl group, carboxyphenyl group Group, methyloxycarbonylphenyl group, aminophenyl group, naphthyl group, hydroxynaphthyl group, phenoxynaphthyl group, nitronaphthyl group, cyanonaphthyl group,
X ^{2, which} includes a carboxynaphthyl group, a methyloxycarbonylnaphthyl group, an aminonaphthyl group, a biphenyl group, an anthracenyl group, and the like, is preferably a hydrogen atom, a hydroxyl group, or an optionally substituted aryl group, and more preferably hydrogen. Is an atom. Further, n represents an integer of 2 to 16, and m = 16−n.

Among the compounds represented by the formula (1), the compound having a substituent X ² in the methylene group of adamantane is
For example, by oxidizing a methylene group of adamantane with a strong acid such as sulfuric acid, nitric acid or fuming sulfuric acid to form a carbonyl group and hydrogenating the compound, X ² having a hydroxyl group can be produced. Further, by halogenating this hydroxyl group with chlorine, bromine, iodine or the like, it is possible to produce a compound in which X ² is a halogen atom. X ² is an alkyl group, an aryl group, an alkoxy group, by reacting an alkyllithium having 1 to 6 carbon atoms, an aryllithium, an alcohol having 1 to 6 carbon atoms, and a phenol capable of reacting with the halogen atom.
Those that are phenoxy groups can be produced. Among the compounds represented by the formula (1), the compound having a substituent X ¹ in the methylene group of adamantane is, for example, the methylene group of adamantane is oxidized with a strong acid such as sulfuric acid, nitric acid or fuming sulfuric acid, and chlorine, Halogenated with bromine, iodine, etc., and the unsaturated group for the halogen atom and alkynes having 2 to 6 carbon atoms such as ethylene, propylene and butylene, and alkynes having 2 to 6 carbon atoms such as acetylene and propyne. The hydrogen atom bonded to the group represented by the formulas (2) to (3) reacts with a hydrogen atom directly bonded to Y ¹ , Ar ¹ , Y ² or Ar ² activated with lithium or the like. Can be manufactured by.

Further, among the compounds represented by the formula (1),
The compound having a substituent X ¹ and / or X ² on the cross-linking methine group of adamantane is, for example, halogenated the cross-linking methine group of adamantane with chlorine, bromine, iodine or the like to obtain X ¹ -H and / or X ^2-. It can be produced by reacting with H to produce X ¹ -H and / or
Alternatively, the hydrogen atom of X ² —H may be lithium, aluminum,
It may be activated with a metal ion such as titanium or antimony.

Among the above coupling reactions, the reaction for producing a compound having a substituent X ¹ on the cross-linked methine group is
Aluminum chloride, tin chloride, antimony chloride, titanium chloride, aluminum bromide, tin bromide, antimony bromide,
It is preferable to use a Lewis acid such as titanium bromide as a catalyst, and it is more preferable to coexist with t-butyl chloride, t-butyl bromide, t-butyl iodide and the like in addition to the catalyst.

As the adamantane derivative as a starting material, adamantane is industrially easily available and the methine group of the adamantane molecule has high reactivity. Therefore, the compound represented by the formula (1) is preferably the following compound. It is particularly preferable that the number of X ¹ groups is 2 to 3 per 1 molecule of adamantane because it can be easily produced.

The coating liquid for forming an insulating film of the present invention has the formula (1)
A compound represented by, a resin obtained by polymerizing the compound,
Alternatively, it can be obtained by dissolving these mixtures in an organic solvent. As a method of polymerizing the compound represented by the formula (1), a known polymerization method can be applied, and examples thereof include radical initiation of benzoyl peroxide, t-butyl peroxide, azobisisobutyronitrile, and the like. Radical polymerization with agents, cationic polymerization with catalysts such as sulfuric acid, phosphoric acid, triethylaluminum, and tagsten chloride, anionic polymerization with catalysts such as lithium naphthalene,
Examples thereof include photoradical polymerization such as light irradiation.
The polymerization usually proceeds by reacting X ^{1's with} each other. Specific examples of the obtained resin include poly (diethynyl adamantane), poly (triethynyl adamantane),
Poly (tetraethynyladamantane) Poly (bis (ethynylphenyl) adamantane), Poly (tris (ethynylphenyl) adamantane), Poly (bis (diethynylphenyl) adamantane), Poly (tris (diethynylphenyl) adamantane), Poly ( And bis (ethynylphenylethynyl) adamantane) and poly (tris (ethynylphenylethynyl) adamantane).

The organic solvent used is not particularly limited, but examples thereof include alcohol solvents such as methanol, ethanol, isopropanol, 1-butanol, 2-butanol, 1-hexanol, 2-ethoxymethanol and 3-methoxypropanol; acetylacetone. , Methyl ethyl ketone, methyl isobutyl ketone, 2-pentanone, 3-pentanone, 2-heptanone, 3-heptanone and other ketone solvents; ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, ethyl propionate, propyl propionate , Ester solvents such as butyl propionate, isobutyl propionate, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, γ-butyrolactone; diisopropyl ether, dibutyl ether Ether-based solvents such as vinyl ether, ethyl propyl ether, anisole, phenetol, and veratrol; aromatic hydrocarbon solvents such as mesitylene, ethylbenzene, diethylbenzene, and propylbenzene are industrially available, and are suitable as solvents because they are safe. These may be used alone or in admixture of two or more.

Further, the coating liquid for forming an insulating film of the present invention comprises
Additives such as radical generators, nonionic surfactants, fluorine-based nonionic surfactants, silane coupling agents, etc., within a range that does not impair the performance of the compound represented by the formula (1) such as reactivity and coating property. You may add. Examples of the radical generator include t-butyl peroxide, pentyl peroxide, hexyl peroxide, lauroyl peroxide, benzoyl peroxide, azobisisobutyronitrile and the like. Examples of the nonionic surfactant include octyl polyethylene oxide, decyl polyethylene oxide, dodecyl polyethylene oxide, octyl polypropylene oxide, decyl polypropylene oxide, and dodecyl polypropylene oxide.
Examples of the fluorine-based nonionic surfactant include perfluorooctyl polyethylene oxide, perfluorodecyl polyethylene oxide, perfluorododecyl polyethylene oxide and the like. As the silane coupling agent, for example, vinyltrimethoxysilane, allyltrimethoxysilane, vinyltriethoxysilane, allyltriethoxysilane, divinyldiethoxysilane,
Examples thereof include trivinylethoxysilane. A foaming agent may be added to the insulating film-forming coating liquid of the present invention, and a porous insulating film can be obtained by adding the foaming agent. Here, as the foaming agent used,
For example, commercially available foaming agents such as vinylpol, cellular, neocerbon, spancell (above, manufactured by Eiwa Chemical Co., Ltd.), fine blow (manufactured by Mitsubishi Chemical), uniform (manufactured by Otsuka Chemical), or easily decomposed as described in JP 2001-181577A. And the like.

The coating solution for forming an insulating film of the present invention is applied to a substrate by any method such as a spin coating method, a roller coating method, a dip coating method and a scanning method, and then the solvent is removed by heat treatment. An insulating film can be formed. The heating method is not particularly limited, but commonly used hot plate heating, furnace method, RTP (Rapid)
A light irradiation heating using a xenon lamp by a Thermal Processor or the like can be applied.

As a result of coupling of X ^1's by heat treatment to form a three-dimensional structure, it becomes possible to form an insulating film having excellent mechanical strength and heat resistance. The temperature of the heat treatment is preferably 200 to 450 ° C, more preferably 250 to 4
It is 00 ° C., and the heating time is usually 1 minute to 10 hours. The obtained insulating film preferably has a relative dielectric constant of 2.5 or less, and is useful for high-speed arithmetic device applications.

[0029]

EXAMPLES The present invention will be described in more detail based on examples, but it goes without saying that the present invention is not limited to the examples.

Production Example 1 2.72 g (20 mmol) of adamantane in a 300 ml four-necked flask,
55.3 g (400 mmol) of t-butyl bromide and 14.2 g (80 mmol) of diphenylacetylene were charged, and the mixture was stirred at room temperature and dissolved. Then, 0.53 g of anhydrous aluminum chloride was added little by little over 1 hour. After stirring at room temperature for 1 hour, the internal temperature was raised to 50 ° C. and the reaction was carried out for 1 hour. After cooling, dilute with 200 g of methylene chloride and dissolve 200 ml of concentrated hydrochloric acid in 200 g of ice water.
I put it in. After separating the hydrochloric acid layer, the methylene chloride layer was washed with saturated brine and washed with water. The methylene chloride layer was concentrated to 20 g, poured into 200 g of methanol, the precipitated crystals were filtered, and dried under reduced pressure at 50 ° C. for 8 hours to obtain 4.67 g of bis (phenylethynylphenyl) adamantane. This was dissolved so that the solid content was 10%. This is referred to as solution a.

Production Example 2 In a 200 ml four-necked flask, 5.0 g of dibromoadamantane (17 m
mol), aluminum bromide 2.3 g (9 mmol) and m-dibromobenzene 100 mL were charged, and the mixture was stirred at 60 ° C. for 10 hours. After cooling, the reaction solution was added to 150 g of ice water in which 10 g of concentrated hydrochloric acid was dissolved, and after stirring, the aqueous phase was removed. After removing excess dibromobenzene by distillation under reduced pressure, 100 mL of methylene chloride was added and dissolved in the residue, washed with water and brine, and dried over magnesium sulfate. After filtering off the desiccant, methylene chloride was concentrated with an evaporator, 100 mL of methanol was added, and the mixture was stirred. The precipitated crystals were filtered out and dried under reduced pressure. This crystal
6.0 g was placed in a 200 mL four-necked flask, 200 mg of dichlorobis (triphenylphosphine) palladium, 400 mg of triphenylphosphine, 180 mg of copper (I) iodide and 100 mL of triethylamine were added, and the temperature was raised to 70 to 80 ° C. Trimethylsilylacetylene 6.7g was added dropwise over 1 hour,
The reaction was carried out at the same temperature for 4 hours. After cooling, the solvent was distilled off, 200 mL of diethyl ether was added to the residue, and the insoluble salt was filtered. The filtrate was washed with 1N hydrochloric acid, saturated saline and ultrapure water, and the ether phase was dried over magnesium sulfate. The desiccant was filtered off, the ether was distilled off, and the residue was produced with a column (stationary phase; silica gel 60, developing solution: hexane / methylene chloride). Dissolve 5.9 g of the main product in 150 mL of methanol and 100 mL of tetrahydrofuran, 0.5 g of potassium carbonate
Was added, and the mixture was stirred at room temperature for 4 hours. The solvent was distilled off under reduced pressure, 200 mL of methylene chloride and 100 mL of 1N hydrochloric acid were added to the residue, and after stirring, the hydrochloric acid phase was removed. 100 mL of ultrapure water for methylene chloride phase
It was washed 3 times with water, the solvent was distilled off from the methylene chloride phase, and the residue was dried under reduced pressure to obtain 3.2 g of bis (diethynylphenyl) adamantane. This was dissolved with anisole to a solid content of 10%. This is referred to as solution b.

Production Example 3 Bis (dibromophenyl) adamantane was obtained in the same manner as in Production Example 2, and 6.0 g of this crystal was placed in a 200 mL four-necked flask and 200 mg of dichlorobis (triphenylphosphine) palladium, 400 mg of triphenylphosphine, and copper iodide. (I) 180 mg and triethylamine 100 mL were added to 70-80
The temperature was raised to ° C. 8.0 g of ethynylbenzene was added dropwise over 1 hour, and the reaction was carried out at the same temperature for 4 hours. After cooling, the solvent was distilled off, 200 mL of diethyl ether was added to the residue, and the insoluble salt was filtered. The filtrate was washed with 1N hydrochloric acid, saturated saline and ultrapure water, and the ether phase was dried over magnesium sulfate.
The desiccant was filtered off, the ether was distilled off, and the residue was produced with a column (stationary phase; silica gel 60, developing solution: hexane / methylene chloride). Add 200 mL of methanol to the main product,
After stirring, the precipitated crystals are filtered, dried under reduced pressure, and bis [(diphenylethynyl) phenyl]] adamantane 5.
8g was obtained. This was dissolved with anisole to a solid content of 10%. This is designated as solution c.

Production Example 4 The same treatment as in Production Example 2 was carried out except that 1-bromobiphenyl was used in place of m-dibromobenzene to obtain 0.7 g of bis (ethynylbiphenyl) adamantane. This was dissolved with anisole to a solid content of 10%. This is referred to as solution d.

Production Example 5 The same treatment as in Production Example 2 was carried out except that dibromoadamantane was changed to tribromoadamantane to obtain 4.5 g of tris (diethynylphenyl) adamantane. This was dissolved with anisole to a solid content of 10%. This is referred to as solution e.

Production Example 6 The same treatment as in Production Example 3 was carried out except that trimethylsilylacetylene was changed to a mixture of 3.3 g of trimethylsilylacetylene and 3.5 g of ethynylbenzene to obtain 6.9 g of bis [ethynyl (phenylethynyl) phenyl] adamantane. . This was dissolved with anisole to a solid content of 10%.
This is referred to as solution f.

Production Example 7 Reference (AAMarik et al., J.Polym.Sci.PART A Polym.Ch
Em., Vol. 30, 1747-1757, 1992), triethynyl adamantane was obtained. This was dissolved in anisole so as to have a solid content of 10% and stirred at 140 to 150 ° C. for 10 hours to obtain a polytriethynyl adamantane solution having a polystyrene reduced weight average molecular weight of 4,200. This is designated as solution g.

Production Example 8 5.8 g (20 mmol) of dibromoadamantane, 10.2 of styrene
g (100 mmol), potassium carbonate 10 g and 10% palladium /
Dissolve 1.0 g of carbon in 100 mL of dimethylacetamide, and
The reaction was carried out at 00 ° C for 8 hours. After cooling, the reaction solution was filtered under reduced pressure through Celite. 250 mL of methylene chloride was added to the filtrate, washed with 100 mL of 2N hydrochloric acid, washed with 200 mL of ultrapure water three times, and the methylene chloride phase was dried over magnesium sulfate.
After the desiccant was filtered off, the methylene chloride phase was concentrated to about 40 mL, and this was added dropwise to 500 mL of methanol. The precipitated crystals were separated by filtration and dried under reduced pressure to obtain 8.5 g of bisstyryl adamantane. This was dissolved with anisole to a solid content of 10%. This is referred to as solution h.

Examples 1 to 8 Anisole solutions obtained in Production Examples 1 to 8 were filtered with a 0.2 μm filter to prepare coating solutions. The obtained coating solution was spin-coated on a 4-inch silicon wafer at a rotation speed of 2000 rpm, prebaked at 150 ° C. for 1 minute, and further heat-treated under a nitrogen atmosphere under the conditions shown in Table 1. The relative dielectric constant of the obtained insulating film was measured by the mercury probe method (Japan SSM SSM495). The results are shown in Table 1.

[0039]

[Table 1]

[0040]

According to the present invention, it becomes possible to provide an insulating film forming coating liquid capable of forming an insulating film having a low relative dielectric constant.

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) H01B 3/44 H01B 3/44 J H01L 21/312 H01L 21/312 A F term (reference) 4J038 CN001 CR061 GA12 MA07 NA21 PA19 5F058 AC10 AF04 AG01 AH02 5G305 AA07 AA11 AB10 BA09 CA34 DA22

Claims (8)

[Claims] 1. An insulating film comprising at least one selected from the group consisting of a compound represented by the formula (1) and a resin obtained by polymerizing the compound represented by the formula (1). Forming coating liquid. (1) (In the formula, X ¹ is an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a monovalent organic group represented by formula (2), or represented by formula (3). Represents a monovalent organic group,
They may be the same or different from each other, and X ² represents a hydrogen atom or a halogen atom, a hydroxyl group, or a carbon number of 1 to 6
Represents an alkyl group, an alkyloxy group having 1 to 6 carbon atoms, a phenoxy group, or an aryl group which may be substituted, and when there are a plurality of groups, they may be the same or different from each other,
n represents an integer of 2 to 16 and m = 16-n. ) —Y ¹ —Ar ¹ (2) (In the formula, Y ¹ represents an alkenylene group having 2 to 6 carbon atoms or an alkynylene group having 2 to 6 carbon atoms, and Ar ¹ represents an aryl group which may be substituted. ^{represents) -Y 2 -Ar 2 -. (} Y 3 -A) p (3) ( wherein, Y ² is a direct bond, an alkylene group having 1 to 6 carbon atoms, an alkenylene group having 2 to 6 carbon atoms or, 2 to 2 carbon atoms
6 represents an alkynylene group, Y ³ represents an alkylene group having 1 to 6 carbon atoms, an alkenylene group having 2 to 6 carbon atoms, or an alkynylene group having 2 to 6 carbon atoms, and either Y ² or Y ³ is present. Alkenylene group having 2 to 6 carbon atoms or 2 carbon atoms
To 6 are alkynylene groups, p is an integer of 1 to 5, Ar ² represents an optionally substituted arylene group, and A represents a hydrogen atom or an optionally substituted aryl group. , P is 2 or more, Y ³ and A may be the same or different. ) 2. X ¹ is an alkynyl group having 2 to 6 carbon atoms, Y ¹
Is a monovalent organic group represented by the formula (2) in which is an alkynylene group having 2 to 6 carbon atoms, or is represented by the formula (3) in which either Y ² or Y ³ is an alkynylene group having 2 to 6 carbon atoms. The coating liquid according to claim 1, which is a monovalent organic group. 3. The coating solution according to claim 1, wherein X ¹ is a monovalent organic group selected from the following group. (In the formula, Ar ¹ , Ar ² , A and p represent the same as above.) 4. The coating liquid according to claim 1, wherein X ¹ is a monovalent organic group selected from the following group. (In the formula, q, r, s, and t each independently represent an integer of 0 to 5, q + r is 1 to 5, and s + t is 0.
~ 5. ) 5. The coating liquid according to claim 1, wherein X ¹ is a monovalent organic group selected from the following group. 6. The coating liquid according to claim 1, wherein the compound represented by the formula (1) is a compound selected from the following formulas. (In the formula, X ¹ represents the same group as described above.) 7. A method for forming an insulating film, which comprises applying the coating liquid according to claim 1 to a substrate and heat-treating the substrate. 8. A method for forming an insulating film, which comprises applying the coating liquid according to claim 1 to a substrate, heat-treating it, and performing three-dimensional crosslinking.