JP2009046540A - Composition for forming film, film and electronic device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for forming a film capable of forming a film that exhibits high heat resistance, high mechanical strengths, a low dielectric constant and good preservation stability with time, a film obtained using the composition for forming a film, and an electronic device comprising the film. <P>SOLUTION: The composition for forming a film comprises a compound represented by formula (1) and/or a polymer obtained by polymerizing at least the compound represented by formula (1). The film is formed using the composition for forming a film. The electronic device comprises the film. In formula (1), A<SP>1</SP>is a bivalent to tetravalent organic group; A<SP>2</SP>is an alkenyl group or an alkynyl group; Ar is a (2+a1)-valent aryl group; R is a hydrogen atom or a 1-30C alkyl group; a1 is an integer of 1-4; and a2 is an integer of 2-4. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a film forming composition, a film obtained using the film forming composition, and an electronic device having the film.

  In recent years, in the field of electronic materials, with the progress of higher integration, more functions, and higher performance, circuit resistance and capacitor capacity between wirings have increased, leading to an increase in power consumption and delay time. In particular, an increase in delay time is a major factor in reducing the signal speed of the device and the occurrence of crosstalk. Therefore, in order to reduce the delay time and speed up the device, it is necessary to reduce parasitic resistance and parasitic capacitance. It has been. As a specific measure for reducing this parasitic capacitance, an attempt has been made to cover the periphery of the wiring with a low dielectric interlayer insulating film. Further, the interlayer insulating film is required to have excellent heat resistance that can withstand post-processes such as a thin film formation process, chip connection, and pinning when manufacturing a mounting substrate, and chemical resistance that can withstand a wet process. Furthermore, in recent years, low resistance Cu wiring is being introduced from Al wiring, and along with this, planarization by CMP (Chemical Mechanical Polishing) has become common, and high mechanical strength that can withstand this process is high. It has been demanded.

  In general, a polymer composed of a saturated hydrocarbon is given as a compound showing a low dielectric constant. Since these polymers have a lower molar polarization than polymers composed of heteroatom-containing units and aromatic hydrocarbon units, they exhibit a lower dielectric constant. However, highly flexible hydrocarbons such as polyethylene, for example, have insufficient heat resistance and cannot be used for electronic device applications.

  On the other hand, polymers in which adamantane and diamantane, which are rigid hydrocarbons having a rigid cage structure, are introduced into the molecule are disclosed, and are disclosed to have a low dielectric constant (Patent Document 1). Most of these materials are designed to introduce vacancies in the film in order to aim for a low dielectric constant. For this reason, there are known problems such as a decrease in heat resistance and mechanical strength, or water adsorbing in the pores, and these problems have been problems to be solved.

JP 2003-292878 A

  The object of the present invention is obtained by using a film-forming composition capable of forming a film having high heat resistance, high mechanical strength, low dielectric constant, and good storage stability, and the film-forming composition. And an electronic device having the film.

As a result of intensive studies, the present inventors have found that the above problems are solved by the following <1>, <9>, and <11> configurations. It is shown below with <2>-<8> and <10> which are preferable embodiments.
<1> A film-forming composition comprising a compound obtained by polymerizing at least a compound represented by the following formula (1) and / or a compound represented by the following formula (1):

（式（１）中、Ａ^１は２〜４価の有機基を表し、Ａ^２はアルケニル基又はアルキニル基を表し、Ａｒは（２＋ａ１）価のアリール基を表し、Ｒは水素原子又は炭素数１〜３０のアルキル基を表し、ａ１は１〜４の整数を表し、ａ２は２〜４の整数を表す。）
＜２＞ 絶縁膜形成用である上記＜１＞に記載の膜形成用組成物、
＜３＞ カゴ型構造を有する化合物、及び／又は、カゴ型構造を有する重合体を含む上記＜１＞又は＜２＞に記載の膜形成用組成物、
＜４＞ カゴ型構造を有する重合体を含む上記＜１＞〜＜３＞のいずれか１つに記載の膜形成用組成物、
＜５＞ 前記カゴ型構造を有する重合体が、カゴ型構造を有するモノマーをラジカル開始剤存在下又は遷移金属触媒存在下で重合して得られたものである上記＜４＞に記載の膜形成用組成物、
＜６＞ 前記カゴ型構造を有するモノマーが、重合可能な炭素−炭素二重結合及び／又は炭素−炭素三重結合を有する上記＜５＞に記載の膜形成用組成物、
＜７＞ 前記カゴ型構造が、アダマンタン、ビアダマンタン、ジアマンタン、トリアマンタン及びテトラマンタンよりなる群から選択される構造である上記＜３＞〜＜６＞のいずれか１つに記載の膜形成用組成物、
＜８＞ 前記カゴ型構造を有するモノマーが、下記式（２）〜（７）で表されるモノマーよりなる群から選択されるモノマーである上記＜５＞又は＜６＞に記載の膜形成用組成物、

(In Formula (1), A ¹ represents a divalent to tetravalent organic group, A ² represents an alkenyl group or an alkynyl group, Ar represents a (2 + a1) valent aryl group, and R represents a hydrogen atom or a carbon number. A 1 represents an integer of 1-4, a2 represents an integer of 2-4.
<2> The film forming composition according to <1>, which is for forming an insulating film,
<3> The film-forming composition as described in <1> or <2> above, comprising a compound having a cage structure and / or a polymer having a cage structure,
<4> The film-forming composition according to any one of the above <1> to <3>, comprising a polymer having a cage structure,
<5> The film formation according to <4>, wherein the polymer having a cage structure is obtained by polymerizing a monomer having a cage structure in the presence of a radical initiator or a transition metal catalyst. Composition,
<6> The film forming composition according to <5>, wherein the monomer having a cage structure has a polymerizable carbon-carbon double bond and / or carbon-carbon triple bond,
<7> For film formation according to any one of <3> to <6>, wherein the cage structure is a structure selected from the group consisting of adamantane, biadamantane, diamantane, triamantane, and tetramantane. Composition,
<8> For film formation according to <5> or <6>, wherein the monomer having a cage structure is a monomer selected from the group consisting of monomers represented by the following formulas (2) to (7): Composition,

（式（２）〜（７）中、Ｘ_１〜Ｘ_８はそれぞれ独立に、水素原子、アルキル基、アルケニル基、アルキニル基、アリール基、シリル基、アシル基、アルコキシカルボニル基又はカルバモイル基を表し、Ｙ_１〜Ｙ_８はそれぞれ独立に、ハロゲン原子、アルキル基、アリール基又はシリル基を表し、ｍ_１、ｍ_５は１〜１６の整数を表し、ｎ_１、ｎ_５は０〜１５の整数を表し、ｍ_２、ｍ_３、ｍ_６、ｍ_７はそれぞれ独立に１〜１５の整数を表し、ｎ_２、n_３、ｎ_６、ｎ_７は０〜１４の整数を表し、ｍ_４、ｍ_８は１〜２０の整数を表し、ｎ_４、ｎ_８は０〜１９の整数を表す。）
＜９＞ 上記＜１＞〜＜８＞のいずれか１つに記載の膜形成用組成物を用いて得られる膜、
＜１０＞ 絶縁膜である上記＜９＞に記載の膜、
＜１１＞ 上記＜９＞又は＜１０＞に記載の膜を有する電子デバイス。

(In the formulas (2) to (7), X _{1 to} X ₈ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a silyl group, an acyl group, an alkoxycarbonyl group or a carbamoyl group. , Y _{1 to} Y ₈ each independently represents a halogen atom, an alkyl group, an aryl group or a silyl group, m ₁ and m ₅ represent an integer of ₁ to 16, and n ₁ and n ₅ represent an integer of 0 to 15 M ₂ , m ₃ , m ₆ and m ₇ each independently represent an integer of 1 to 15, n ₂ , n ₃ , n ₆ and n ₇ represent an integer of 0 to 14, m ₄ , m ₈ represents an integer of 1 to 20, and n ₄ and n ₈ represent an integer of 0 to 19.)
<9> A film obtained using the film forming composition according to any one of <1> to <8> above,
<10> The film according to <9>, which is an insulating film,
<11> An electronic device having the film according to <9> or <10>.

  According to the present invention, a film-forming composition capable of forming a film having high heat resistance, high mechanical strength, low dielectric constant, and good storage stability, and obtained using the film-forming composition. And an electronic device having the film can be provided.

Hereinafter, the present invention will be described in detail.
The film forming composition of the present invention is characterized by containing a polymer obtained by polymerizing at least a compound represented by the following formula (1) and / or a compound represented by the following formula (1).
The film forming composition of the present invention can be suitably used as an insulating film forming composition.

（式（１）中、Ａ^１は２〜４価の有機基を表し、Ａ^２はアルケニル基又はアルキニル基を表し、Ａｒは（２＋ａ１）価のアリール基を表し、Ｒは水素原子又は炭素数１〜３０のアルキル基を表し、ａ１は１〜４の整数を表し、ａ２は２〜４の整数を表す。）

(In Formula (1), A ¹ represents a divalent to tetravalent organic group, A ² represents an alkenyl group or an alkynyl group, Ar represents a (2 + a1) valent aryl group, and R represents a hydrogen atom or a carbon number. A 1 represents an integer of 1-4, a2 represents an integer of 2-4.

(Compound represented by the formula (1))
The film-forming composition of the present invention contains a polymer obtained by polymerizing at least a compound represented by the formula (1) and / or a compound represented by the formula (1).
In the compound represented by the formula (1), the amide bond in the molecule and COOR react with heat to form an imide ring and become highly heat-resistant. Heat resistance can be improved.
In the present invention, the “polymer represented by at least the compound represented by the formula (1) and / or the compound represented by the formula (1)” is also collectively referred to as “compound (1)”. .

A ¹ in the formula (1) is a divalent to tetravalent organic group.
A ¹ in formula (1) is preferably a group having an aromatic ring and / or an aliphatic ring in order to obtain a more excellent effect of the present invention, and a hydrogen atom at an arbitrary position from the aromatic ring or the aliphatic ring. Or a hydrogen atom at any position from a structure in which two or more structures selected from the group consisting of an aromatic ring, an aliphatic ring, a linear alkylene group, a branched alkylene group and an ether bond are linked. A group obtained by removing 2 to 4 atoms is more preferable. The aromatic ring and the aliphatic ring include a condensed aromatic ring, a condensed aliphatic ring, and a condensed ring of an aromatic ring and an aliphatic ring. The aromatic ring or the aliphatic ring is preferably a 6-membered ring. By having the ring structure, it is preferable from the viewpoint of high heat resistance.
The element constituting A ¹ is preferably carbon and hydrogen, or one or more elements selected from the group consisting of carbon, hydrogen, oxygen, nitrogen, sulfur and fluorine. And hydrogen, or carbon, hydrogen and oxygen are more preferable. A ¹ is preferably a group composed of carbon and hydrogen, or carbon, hydrogen and oxygen, from the viewpoint that it is difficult to increase the initial k value as compared with other elements.

Specific examples of A ¹ below. In the following specific examples, the substitution position of the amide bond moiety in formula (1) may be any position, and A ¹ is a group obtained by removing 2 to 4 hydrogen atoms at any position from the following specific examples. Preferably there is.

Among these, A ¹ is more preferably a group obtained by removing 2 to 4 hydrogen atoms at arbitrary positions from the following specific examples.

A ² in the formula (1) represents an alkenyl group or an alkynyl group, and is preferably a vinyl group or an ethynyl group.
If the equation a1 and / or a2 in (1) is an integer of 2 or more, A ² that there exist a plurality are each independently, an alkenyl group can be selected alkynyl group.
Further, the carbon from A ² in the compound represented by formula (1) - carbon unsaturated bonds, all of which, carbon - carbon double bond or carbon - is preferably either carbon triple bond, More preferably, all of them are either vinyl groups or ethynyl groups.

Ar in the formula (1) represents a (2 + a1) -valent aryl group.
In the formula (1), when a2 is an integer of 2 or more, a plurality of Ars may be different from or different from other Ars in the same molecule.
Ar is preferably a group obtained by removing (2 + a1) hydrogen atoms from an aromatic ring, and (2 + a1) hydrogen atoms are removed from an aromatic ring selected from the group consisting of benzene, biphenyl, naphthalene and anthracene. More preferably a group obtained by removing (2 + a1) hydrogen atoms from an aromatic ring selected from the group consisting of benzene, biphenyl and naphthalene, and (2 + a1) hydrogen atoms from benzene. Particularly preferred is a group excluding.

R in the formula (1) represents a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, and is preferably a hydrogen atom or an alkyl group having 5 to 30 carbon atoms, and a hydrogen atom or an alkyl group having 8 to 20 carbon atoms. It is more preferably a group, and further preferably an alkyl group having 8 to 20 carbon atoms. Moreover, the alkyl group in R may be a straight chain or may have a branch.
In the formula (1), when a2 is an integer of 2 or more, a plurality of Rs may be different from or different from other Rs in the same molecule.

A1 in the formula (1) represents an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 1 or 2.
A2 in the formula (1) represents an integer of 2 to 4, and is preferably 2 or 3.

The molecular weight of the compound represented by the formula (1) is preferably 300 or more. If it is 300 or more, since the volatility is low, the concentration in the film does not decrease, and the target function is sufficiently developed.
The molecular weight of the compound represented by the formula (1) is preferably 2,000 or less.

Although the preferable specific example (C-1 to C-162) of the compound shown by Formula (1) which can be used for this invention below is described, this invention is not limited to these.
In the following specific examples, only examples in which R is a hydrogen atom are described, but those in which R is a linear or branched alkyl group having 1 to 30 carbon atoms can also be preferably exemplified.

The amount of the compound represented by the formula (1) in the film-forming composition of the present invention is preferably 0.1 to 80% by weight with respect to the solid content of the film-forming composition. More preferably, it is 5% by weight, and particularly preferably 5 to 50% by weight. Here, the solid content corresponds to all components constituting the film obtained using this composition.
Moreover, the compound shown by Formula (1) in the composition for film formation of this invention may be used individually by 1 type, or may use 2 or more types together.

(Polymer polymerized using at least compound represented by formula (1))
The film-forming composition of the present invention contains a polymer obtained by polymerizing at least a compound represented by the formula (1) and / or a compound represented by the formula (1).
The polymer polymerized using at least the compound represented by the formula (1) reacts with the amide bond in the molecule and COOR by heat to form an imide ring and becomes highly heat resistant. The heat resistance of the film can be further improved by heating.
The polymer polymerized using at least the compound represented by formula (1) is preferably a polymer obtained by polymerizing only the compound represented by formula (1).
The preferred compound in the compound represented by the formula (1) used for the polymer is the same as the preferred compound in the compound represented by the formula (1) described above.
The compound represented by the formula (1) used for the polymer may be used alone or in combination of two or more.

  The method for producing a polymer obtained by polymerization using at least the compound represented by the formula (1) is not particularly limited, but a step of polymerizing at least the compound represented by the formula (1) in the presence of a polymerization initiator. Is preferable, and a method including a step of polymerizing at least the compound represented by the formula (1) in the presence of a radical initiator or in the presence of a transition metal catalyst is more preferable.

As the radical polymerization initiator, an organic peroxide or an organic azo compound is preferably used, and an organic peroxide is particularly preferable.
Examples of the organic peroxide include ketone peroxides such as perhexa H, peroxyketals such as perhexa TMH, hydroperoxides such as perbutyl H-69, park mill D, and perbutyl C, which are commercially available from Nippon Oil & Fats Co., Ltd. Dialkyl peroxides such as perbutyl D, diacyl peroxides such as niper BW, peroxyesters such as perbutyl Z and perbutyl L, and peroxydicarbonates such as peroyl TCP are preferably used.
Examples of the organic azo compound include azonitrile compounds such as V-30, V-40, V-59, V-60, V-65, and V-70 that are commercially available from Wako Pure Chemical Industries, Ltd., VA-080. , Azoamide compounds such as VA-085, VA-086, VF-096, VAm-110, VAm-111, cyclic azoamidine compounds such as VA-044, VA-061, and azoamidines such as V-50, VA-057 Compounds and the like are preferably used.

Only one polymerization initiator may be used, or two or more polymerization initiators may be mixed and used.
The amount of the polymerization initiator used is preferably 0.001 to 2 moles relative to 1 mole of the total moles of the compound represented by the formula (1) and other polymerizable compounds, and 0.01 to 1 mole. It is more preferable that it is 0.05-0.5 mol.

The polymerization reaction of the monomer is also preferably performed in the presence of a transition metal catalyst.
Examples of the transition metal catalyst include Pd-based catalysts such as tetrakistriphenylphosphine palladium (Pd (PPh ₃ ) ₄ ) and palladium acetate (Pd (OAc) ₂ ), Ni-based catalysts such as Ziegler-Natta catalyst, nickel acetylacetonate, etc. catalyst, W-based catalyst such as WCl _6, Mo-based catalysts such as MoCl _5, Ta catalysts such as TaCl _5, Nb-based catalyst such as NbCl _5, Rh-based catalyst, Pt-based catalysts, and the like preferably.

Only one transition metal catalyst or a mixture of two or more transition metal catalysts may be used.
The amount of the transition metal catalyst used is preferably 0.001 to 2 mol, more preferably 0.01 to 1 mol, per 1 mol of the total number of moles of the compound represented by formula (1) and other polymerizable compounds The amount is particularly preferably 0.05 to 0.5 mol.

(Compound having a cage structure, polymer having a cage structure)
The film-forming composition of the present invention preferably contains a compound having a cage structure and / or a polymer having a cage structure.
The “cage structure” in the present invention is a structure in which the volume is determined by a plurality of rings formed of covalently bonded atoms, and a point located within the volume cannot be separated from the volume without passing through the ring. Point to.
For example, an adamantane structure is considered a cage structure. In contrast, a cyclic structure having a single bridge, such as norbornane (bicyclo [2.2.1] heptane), is not considered a cage structure because the ring of the single bridged cyclic compound does not define volume. .

  The cage structure may include any of saturated and unsaturated bonds, and may include heteroatoms such as oxygen, nitrogen, and sulfur, but is preferably a cage structure composed of hydrocarbons. From the viewpoint of low dielectric constant, a cage structure made of saturated hydrocarbon is more preferable.

  The cage structure in the present invention includes an adamantane structure, a biadamantane structure, a diamantane structure, a bi (diamantane) structure, a triamantane structure, and a tetramantane structure. ) Structure or dodecahedrane structure, preferably adamantane structure, biadamantane structure, diamantane structure, triamantane structure or tetramantane structure, and preferably an adamantane structure, biadamantane structure or diamantane structure Is more preferable, and a biadamantan structure or a diamantane structure is particularly preferable in that it has a low dielectric constant.

  The structure is shown below. The dodecahedrane structure is a dodecahedron hydrocarbon structure in which 20 vertices of the dodecahedron are each a carbon atom. Moreover, although the connection part of two adamantane structures in a biadamantan structure should just be arbitrary positions, it is preferable to connect with bridge head positions. Similarly, in the bi (diamantane) structure, the connecting portion of the two diamantane structures may be at any position, but is preferably connected at the bridge head positions.

The cage structure may have one or more substituents.
Examples of the substituent include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms (methyl, t-butyl, cyclopentyl, cyclohexyl, etc.) , Alkenyl groups having 2 to 10 carbon atoms (vinyl, propenyl, etc.), alkynyl groups having 2 to 10 carbon atoms (ethynyl, phenylethynyl, etc.), aryl groups having 6 to 20 carbon atoms (phenyl, 1-naphthyl, 2-naphthyl) Etc.), an acyl group having 2 to 10 carbon atoms (such as benzoyl), an alkoxycarbonyl group having 2 to 10 carbon atoms (such as methoxycarbonyl), a carbamoyl group having 1 to 10 carbon atoms (such as N, N-diethylcarbamoyl), carbon, etc. An aryloxy group having 6 to 20 carbon atoms (phenoxy or the like), an arylsulfonyl group having 6 to 20 carbon atoms (such as phenylsulfonyl), or a nitro group Cyano group, a silyl group (triethoxysilyl, methyldiethoxysilyl, trivinylsilyl or the like) and the like.

  The cage structure is preferably a divalent to tetravalent group. At this time, the group bonded to the cage structure may be a monovalent or higher valent substituent or a divalent or higher linking group. The cage structure is more preferably a divalent or trivalent group, and particularly preferably a divalent group.

The film-forming composition of the present invention more preferably contains a polymer having a cage structure, and more preferably a monomer polymer having a cage structure.
Here, the term “monomer” refers to a monomer that is polymerized to be a dimer or higher polymer. The polymer may be a homopolymer or a copolymer.

  The polymerization reaction of the monomer is caused by the polymerizable group substituted with the monomer. Here, the polymerizable group refers to a reactive substituent that polymerizes the monomer. The polymerization reaction may be any polymerization reaction, and examples thereof include radical polymerization, cationic polymerization, anionic polymerization, ring-opening polymerization, polycondensation, polyaddition, addition condensation, or transition metal catalyst polymerization.

  The monomer polymerization reaction is preferably performed in the presence of a nonmetallic polymerization initiator. For example, a monomer having a polymerizable carbon-carbon double bond or carbon-carbon triple bond may be polymerized in the presence of a polymerization initiator that exhibits activity by generating free radicals such as carbon radicals and oxygen radicals by heating. it can.

As the radical polymerization initiator, an organic peroxide or an organic azo compound is preferably used, and an organic peroxide is particularly preferable.
As the organic peroxide and the organic azo compound, those described above can be preferably used.

Only one polymerization initiator may be used, or two or more polymerization initiators may be mixed and used.
The amount of the polymerization initiator used is preferably 0.001 to 2 mol, more preferably 0.01 to 1 mol, and 0.05 to 0.5 mol with respect to 1 mol of the monomer. It is particularly preferred.

The polymerization reaction of the monomer is also preferably performed in the presence of a transition metal catalyst. For example, a monomer having a polymerizable carbon-carbon double bond or carbon-carbon triple bond is converted into a Pd-based catalyst such as tetrakistriphenylphosphine palladium (Pd (PPh ₃ ) ₄ ) or palladium acetate (Pd (OAc) ₂ ). , Ziegler-Natta catalyst, Ni catalyst such as nickel acetyl acetonate, W-based catalyst such as WCl _6, Mo-based catalysts such as MoCl _5, Ta catalysts such as TaCl _5, Nb-based catalyst such as NbCl _5, Rh-based Polymerization is preferably performed using a catalyst, a Pt-based catalyst, or the like.

Only one transition metal catalyst or a mixture of two or more transition metal catalysts may be used.
The amount of the transition metal catalyst used is preferably 0.001 to 2 mol, more preferably 0.01 to 1 mol, and particularly preferably 0.05 to 0.5 mol with respect to 1 mol of the monomer.

  The method for producing the polymer having a cage structure is not particularly limited, but is preferably a method including a step of polymerizing using a monomer having a cage structure in the presence of a polymerization initiator. More preferably, the method includes a step of polymerizing using a monomer having a cage structure in the presence or in the presence of a transition metal catalyst.

The cage structure in the present invention may be substituted as a pendant group in the polymer and may be a part of the polymer main chain, but a form that is a part of the polymer main chain is more preferable.
Here, the form which is a part of the polymer main chain means that the polymer chain is cleaved when the cage compound is removed from the polymer. In this form, the cage structure is directly single-bonded or connected by an appropriate divalent linking group. Examples of the linking group include, for example, —C (R ¹¹ ) (R ¹² ) —, —C (R ¹³ ) ═C (R ¹⁴ ) —, —C≡C—, arylene group, —CO—, —O—. , —SO ₂ —, —N (R ¹⁵ ) —, —Si (R ¹⁶ ) (R ¹⁷ ) —, or a combination thereof. Here, R < ¹¹ > -R < ¹⁷ > represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group each independently. These linking groups may be substituted with a substituent, and for example, the above-mentioned substituents are preferable examples.
Among these, more preferred linking groups are —C (R ¹¹ ) (R ¹² ) —, —CH═CH—, —C≡C—, arylene group, —O—, —Si (R ¹⁶ ) (R ¹⁷ ). - or a group formed by combining these groups, particularly preferred are, -C terms of low dielectric constant ^{(R 11) (R 12)} -, - is CH = CH-.

The weight average molecular weight of the polymer having a cage structure is preferably 1,000 to 500,000, more preferably 5,000 to 200,000, and particularly preferably 10,000 to 100,000.
The polymer having a cage structure may be contained in the film-forming composition of the present invention as a resin composition having a molecular weight distribution.
The molecular weight of the compound having a cage structure is preferably 150 to 3,000, more preferably 200 to 2,000, and particularly preferably 220 to 1,000.

  The polymer having a cage structure that can be used in the present invention is preferably a polymer of a monomer having a polymerizable carbon-carbon double bond or carbon-carbon triple bond, represented by the following formulas (2) to ( More preferably, it is a polymer of the compound represented by 7).

（式（２）〜（７）中、Ｘ_１〜Ｘ_８はそれぞれ独立に、水素原子、アルキル基、アルケニル基、アルキニル基、アリール基、シリル基、アシル基、アルコキシカルボニル基又はカルバモイル基等を表し、Ｙ_１〜Ｙ_８はそれぞれ独立に、ハロゲン原子、アルキル基、アリール基又はシリル基を表し、ｍ_１、ｍ_５は１〜１６の整数を表し、ｎ_１、ｎ_５は０〜１５の整数を表し、ｍ_２、ｍ_３、ｍ_６、ｍ_７はそれぞれ独立に１〜１５の整数を表し、ｎ_２、n_３、ｎ_６、ｎ_７は０〜１４の整数を表し、ｍ_４、ｍ_８は１〜２０の整数を表し、ｎ_４、ｎ_８は０〜１９の整数を表す。）

(In formulas (2) to (7), X _{1 to} X ₈ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a silyl group, an acyl group, an alkoxycarbonyl group or a carbamoyl group. Y _{1 to} Y ₈ each independently represents a halogen atom, an alkyl group, an aryl group or a silyl group, m ₁ and m ₅ represent an integer of ₁ to 16, and n ₁ and n ₅ represent 0 to 15 M ₂ , m ₃ , m ₆ and m ₇ each independently represents an integer of 1 to 15, n ₂ , n ₃ , n ₆ and n _{7 each} represents an integer of 0 to 14, m ₄ , m ₈ represents an integer of _{1~20, n 4,} n ₈ is an integer of 0 to 19.)

In formulas (2) to (7), X _{1 to} X ₈ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, An aryl group having 6 to 20 carbon atoms, a silyl group having 0 to 20 carbon atoms, an acyl group having 2 to 10 carbon atoms, an alkoxycarbonyl having 2 to 10 carbon atoms, a carbamoyl group having 1 to 20 carbon atoms and the like are represented. Among these, Preferably a hydrogen atom, a C1-C10 alkyl group, a C6-C20 aryl group, a C0-C20 silyl group, a C2-C10 acyl group, C2-C10 An alkoxycarbonyl group and a carbamoyl group having 1 to 20 carbon atoms, more preferably a hydrogen atom and an aryl group having 6 to 20 carbon atoms, and particularly preferably a hydrogen atom.
In formulas (2) to (7), Y _{1 to} Y ₈ are each independently a halogen atom (fluorine, chlorine, bromine, etc.), an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or carbon. Represents a silyl group having 0 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms which may have a substituent and an aryl group having 6 to 20 carbon atoms, particularly preferably an alkyl group (methyl group). Etc.).
X _{1 to} X ₈ and Y _{1 to} Y ₈ may be further substituted with another substituent.

In formula (2) or formula (5), m ₁ and m ₅ each independently represents an integer of 1 to 16, preferably 1 to 4, more preferably 1 to 3, particularly preferably 2. is there.
In formula (2) or formula (5), n ₁ and n ₅ each independently represents an integer of 0 to 15, preferably 0 to 4, more preferably 0 or 1, particularly preferably 0. is there.
In formula (3) or formula (6), m ₂ , m ₃ , m ₆ and m ₇ each independently represent an integer of 1 to 15, preferably 1 to 4, more preferably 1 to 3. Particularly preferably 2.
In formula (3) or formula (6), n ₂ , n ₃ , n ₆ and n ₇ each independently represents an integer of 0 to 14, preferably 0 to 4, more preferably 0 or 1. Particularly preferably 0.
In formula (4) or formula (7), m ₄ and m ₈ each independently represents an integer of 1 to 20, preferably 1 to 4, more preferably 1 to 3, particularly preferably 2. is there.
In formula (4) or formula (7), n ₄ and n ₈ each independently represent an integer of 0 to 19, preferably 0 to 4, more preferably 0 or 1, particularly preferably 0. is there.

  The monomer having a cage structure that can be used in the present invention is preferably a compound represented by Formula (2), Formula (3), Formula (5), or Formula (6). ) Or a compound represented by formula (3) is more preferred, and a compound represented by formula (3) is particularly preferred.

  The compound having a cage structure that can be used in the present invention and / or the polymer having a cage structure may be used in combination of two or more, and the cage structure that can be used in the present invention. Two or more monomers may be copolymerized.

  The compound having a cage structure and the polymer having a cage structure preferably have sufficient solubility in an organic solvent. The solubility of the compound having a cage structure is preferably 3% by weight or more, more preferably 5% by weight or more, and particularly preferably 10% by weight or more with respect to cyclohexanone or anisole at 25 ° C. .

  Examples of the compound having a cage structure that can be used in the present invention and the polymer having a cage structure include, for example, JP-A-11-322929, JP-A-2003-12802, and JP-A-2004-18593. Polybenzoxazole described in JP-A-2001-2899, quinoline resin described in JP-A No. 2001-2899, JP-T 2003-530464, JP-T 2004-535497, JP-T 2004-504424, JP-T 2004-504455 In Japanese Patent Publication No. 2005-501131, No. 2005-516382, No. 2005-514479, No. 2005-522528, No. 2000-1000080, and US Pat. No. 6,509,415. The polyaryl resin described in JP-A-11-214382 , JP-A-2001-332542, JP-A-2003-252882, JP-A-2003-292878, JP-A-2004-2787, JP-A-2004-67877, JP-A-2004-59444. Polyadamantane, polyimides described in JP-A-2003-252992 and JP-A-2004-26850, and the like.

  Specific examples (M-1 to M-55) of monomers having a cage structure that can be used in the present invention are described below, but the present invention is not limited thereto. In the following specific examples, Et represents an ethyl group.

  Further, examples of the monomer having a cage structure that can be used in the present invention include those in which —C≡C— in the above specific examples is changed to —CH═CH—.

As the solvent used in the polymerization reaction, any solvent may be used as long as the raw material monomer can be dissolved at a necessary concentration and does not adversely affect the characteristics of the film formed from the obtained polymer. . For example, alcohol solvents such as water, methanol, ethanol, propanol, alcohol solvents such as alcohol acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, γ-butyrolactone, methyl benzoate Ester solvents such as dibutyl ether and anisole, toluene, xylene, mesitylene, 1,2,4,5-tetramethylbenzene, pentamethylbenzene, isopropylbenzene, 1,4-diisopropylbenzene, t- Butylbenzene, 1,4-di-t-butylbenzene, 1,3,5-triethylbenzene, 1,3,5-tri-t-butylbenzene, 4-t-butyl-orthoxylene, 1- Aromatic hydrocarbon solvents such as tilnaphthalene and 1,3,5-triisopropylbenzene, amide solvents such as N-methylpyrrolidinone and dimethylacetamide, carbon tetrachloride, dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, Halogen solvents such as 1,2-dichlorobenzene and 1,2,4-trichlorobenzene and aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane can be used.
Among these, more preferred solvents are acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, ethyl acetate, propylene glycol monomethyl ether acetate, γ-butyrolactone, anisole, tetrahydrofuran, toluene, xylene, mesitylene, 1, 2, 4, 5-tetramethylbenzene, isopropylbenzene, t-butylbenzene, 1,4-di-t-butylbenzene, 1,3,5-tri-t-butylbenzene, 4-t-butyl-orthoxylene, 1-methyl Naphthalene, 1,3,5-triisopropylbenzene, 1,2-dichloroethane, chlorobenzene, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene, more preferably tetrahydrofuran, γ-butyrolactone, Nisole, toluene, xylene, mesitylene, isopropylbenzene, t-butylbenzene, 1,3,5-tri-t-butylbenzene, 1-methylnaphthalene, 1,3,5-triisopropylbenzene, 1,2-dichloroethane, Chlorobenzene, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene, particularly preferably γ-butyrolactone, anisole, mesitylene, t-butylbenzene, 1,3,5-triisopropylbenzene, 1,2- Dichlorobenzene and 1,2,4-trichlorobenzene. These may be used alone or in admixture of two or more.
The concentration of the monomer in the reaction solution is preferably 1 to 50% by weight, more preferably 5 to 30% by weight, and particularly preferably 10 to 20% by weight.

Optimum conditions for the polymerization reaction in the present invention vary depending on the polymerization initiator, monomer, solvent type, concentration, and the like, but preferably the internal temperature is 0 ° C to 200 ° C, more preferably 50 ° C to 170 ° C, and particularly preferably 100. C. to 150.degree. C., preferably 1 to 50 hours, more preferably 2 to 20 hours, and particularly preferably 3 to 10 hours.
Moreover, in order to suppress the inactivation of the polymerization initiator by oxygen, it is preferable to make it react under inert gas atmosphere (for example, nitrogen, argon, etc.). The oxygen concentration during the reaction is preferably 100 ppm or less, more preferably 50 ppm or less, and particularly preferably 20 ppm or less.
The preferred range of the weight average molecular weight of the polymer obtained by polymerization is 1,000 to 500,000, more preferably 5,000 to 300,000, and particularly preferably 10,000 to 200,000.

In addition, the compound having a cage structure can be prepared by, for example, using commercially available diamantane as a raw material and reacting with bromine in the presence or absence of an aluminum bromide catalyst to introduce a bromine atom at a desired position, followed by aluminum bromide or aluminum chloride. Synthesis by conducting Friedel-Crafts reaction with vinyl bromide in the presence of Lewis acid such as iron chloride, introducing 2,2-dibromoethyl group, followed by dehydrobration with strong base and conversion to ethynyl group be able to. Specifically, it is synthesized according to the method described in Macromolecules., 1991, 24, 5266-5268, 1995, 28, 5554-5560, Journal of Organic Chemistry., 39, 2995-3003 (1974), etc. can do.
In addition, an alkyl group or a silyl group can be introduced by anionizing a hydrogen atom of a terminal acetylene group with butyllithium or the like and reacting this with an alkyl halide or a silyl halide.

The compound having a cage structure and / or the polymer having a cage structure may be used alone or in combination of two or more. In addition, a compound having a cage structure and a polymer having a cage structure may be used in combination.
The film-forming composition of the present invention preferably contains a compound represented by the formula (1) and a polymer having a cage structure.
When the film-forming composition of the present invention contains a compound having a cage structure and / or a polymer having a cage structure, the compound represented by the formula (1) in the film-forming composition of the present invention, and // The total content of the polymer polymerized using at least the compound represented by formula (1) is the polymer polymerized using at least the compound represented by formula (1) and the compound represented by formula (1). , Preferably 5 to 80% by weight, more preferably 5 to 60% by weight, and more preferably 10 to 60% by weight based on the total weight of the compound having a cage structure and the polymer having a cage structure. % Is more preferable.

  The film-forming composition of the present invention may contain known additives as described later, if necessary, in addition to the above components.

The film forming composition of the present invention preferably has a sufficiently low metal content as an impurity. The metal concentration of the film-forming composition can be measured with high sensitivity by inductively coupled plasma mass spectrometry (ICP-MS), and the metal content other than the transition metal in that case is preferably 30 ppm or less, more preferably Is 3 ppm or less, particularly preferably 300 ppb or less.
In addition, the transition metal has a high catalytic ability to promote oxidation, and from the viewpoint of increasing the dielectric constant of the film obtained in the present invention by an oxidation reaction in the prebaking and thermosetting processes, the content is preferably smaller. Preferably it is 10 ppm or less, More preferably, it is 1 ppm or less, Most preferably, it is 100 ppb or less.
The metal concentration of the film forming composition of the present invention can also be evaluated by performing total reflection fluorescent X-ray measurement on a film obtained using the film forming composition of the present invention.
When a W (tungsten) ray is used as an X-ray source, K, Ca, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, and Pd can be observed as metal elements, each of which is 100 × 10 ¹⁰ atoms. · Cm ⁻² or less is preferable, 50 × 10 ¹⁰ atom · cm ⁻² or less is more preferable, and 10 × 10 ¹⁰ atom · cm ⁻² or less is particularly preferable.
Moreover, Br which is halogen is also observable, and the residual amount is preferably 10,000 × 10 ¹⁰ atom · cm ⁻² or less, more preferably 1,000 × 10 ¹⁰ atom · cm ⁻² or less, and 400 × 10 ^10. Atom · cm ⁻² or less is particularly preferable. Further, although Cl can be observed as a halogen, the residual amount is preferably 100 × 10 ¹⁰ atom · cm ⁻² or less from the viewpoint of damaging the CVD apparatus, the etching apparatus, etc., and 50 × 10 ¹⁰ atom · cm ^−2. The following is more preferable, and 10 × 10 ¹⁰ atom · cm ⁻² or less is particularly preferable.

The film forming composition of the present invention may contain an organic solvent.
Although it does not specifically limit as an organic solvent, For example, alcohol solvents, such as methanol, ethanol, 2-propanol, 1-butanol, 2-ethoxymethanol, 3-methoxypropanol, 1-methoxy-2-propanol, acetone, acetylacetone, Ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, 2-pentanone, 3-pentanone, 2-heptanone, 3-heptanone, cyclopentanone, cyclohexanone, ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, propionic acid Esters such as ethyl, propyl propionate, butyl propionate, isobutyl propionate, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, γ-butyrolactone, diisopropyl Ether solvents such as pyr ether, dibutyl ether, ethyl propyl ether, anisole, phenetol, veratrol, aromatic hydrocarbon solvents such as mesitylene, ethylbenzene, diethylbenzene, propylbenzene, t-butylbenzene, N-methylpyrrolidinone, dimethylacetamide And amide solvents such as these may be used, and these may be used alone or in admixture of two or more.
More preferred organic solvents are 1-methoxy-2-propanol, propanol, acetylacetone, cyclohexanone, propylene glycol monomethyl ether acetate, butyl acetate, methyl lactate, ethyl lactate, γ-butyrolactone, anisole, mesitylene, t-butylbenzene, Particularly preferred organic solvents are 1-methoxy-2-propanol, cyclohexanone, 2-heptanone, propylene glycol monomethyl ether acetate, ethyl lactate, γ-butyrolactone, t-butylbenzene, and anisole.

The solid content concentration of the film-forming composition of the present invention is preferably 1 to 50% by weight, more preferably 2 to 15% by weight, and particularly preferably 3 to 10% by weight.
Here, the solid content corresponds to all components constituting the film obtained using this composition.
The polymer having a cage structure obtained in the present invention preferably has sufficient solubility in an organic solvent. The solubility of the polymer having a cage structure is preferably 3% by weight or more, more preferably 5% by weight or more, and particularly preferably 10% by weight or more with respect to cyclohexanone or anisole at 25 ° C.

  Furthermore, the composition for forming a film of the present invention includes a radical generator, colloidal silica, and the like within a range that does not impair the properties of the obtained insulating film (heat resistance, dielectric constant, mechanical strength, coatability, adhesion, etc.). You may add additives, such as surfactant, a silane coupling agent, and an adhesive agent.

  Any colloidal silica may be used as the colloidal silica that can be used in the present invention. For example, a dispersion in which high-purity silicic acid is dispersed in a hydrophilic organic solvent or water, preferably having an average particle size of 5 to 30 nm, more preferably 10 to 20 nm, and a solid content concentration of 5 to 40% by weight It is.

  As the surfactant that can be used in the present invention, any surfactant may be used. For example, nonionic surfactants, anionic surfactants, cationic surfactants, and the like, silicone surfactants, fluorine-containing surfactants, polyalkylene oxide surfactants, acrylic surfactants Agents. The surfactant that can be used in the present invention may be one type or two or more types. As the surfactant, silicone surfactants, nonionic surfactants, fluorine-containing surfactants, and acrylic surfactants are preferable, and silicone surfactants are particularly preferable.

  The addition amount of the surfactant that can be used in the present invention is preferably 0.01% by weight or more and 1% by weight or less, and preferably 0.1% by weight or more and 0.5% by weight or less with respect to the total amount of the film-forming coating solution. More preferably, it is not more than% by weight.

  In the present invention, the silicone-based surfactant is a surfactant containing at least one Si atom. The silicone-based surfactant that can be used in the present invention may be any silicone-based surfactant, and preferably has a structure containing alkylene oxide and dimethylsiloxane. A structure including the following chemical formula is more preferable.

  In said formula, R is a hydrogen atom or a C1-C5 alkyl group, x is an integer of 1-20, m and n are the integers of 2-100 each independently. Further, when there are a plurality of R, they may be the same or different.

  Examples of silicone surfactants that can be used in the present invention include BYK-306, BYK-307 (manufactured by Big Chemie), SH7PA, SH21PA, SH28PA, SH30PA (manufactured by Toray Dow Corning Silicone), Troysol S366 ( Troy Chemical Co., Ltd.).

  The nonionic surfactant that can be used in the present invention may be any nonionic surfactant. For example, polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene dialkyl esters, sorbitan fatty acid esters, fatty acid-modified polyoxyethylenes, polyoxyethylene-polyoxypropylene block copolymers, etc. Can do.

  The fluorine-containing surfactant that can be used in the present invention may be any fluorine-containing surfactant. For example, perfluorooctyl polyethylene oxide, perfluorodecyl polyethylene oxide, perfluorodecyl polyethylene oxide and the like can be mentioned.

  The acrylic surfactant that can be used in the present invention may be any acrylic surfactant. For example, an acrylic acid copolymer or a methacrylic acid copolymer can be used.

Any silane coupling agent may be used as the silane coupling agent that can be used in the present invention.
Examples of the silane coupling agent include 3-glycidyloxypropyltrimethoxysilane, 3-aminoglycidyloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 1 -Methacryloxypropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3 -Aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarboni -3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-triethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1, 4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N- Bis (oxyethylene) 3-aminopropyltrimethoxysilane, N- bis (oxyethylene) -3-aminopropyltriethoxysilane and the like.
The silane coupling agent that can be used in the present invention may be used alone or in combination of two or more.

Any adhesion promoter may be used as the adhesion promoter that can be used in the present invention.
Examples of the adhesion promoter include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane. , Β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, trimethoxyvinylsilane, γ-aminopropyltriethoxysilane, aluminum monoethylacetoacetate diisopropylate, vinyltris (2-methoxyethoxy) silane, N- (2 -Aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropylto Limethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, chloromethyldimethylchlorosilane, trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane , Dimethylvinylethoxysilane, diphenyldimethoxysilane, phenyltriethoxysilane, hexamethyldisilazane, N, N′-bis (trimethylsilyl) urea, dimethyltrimethylsilylamine, trimethylsilylimidazole, vinyltrichlorosilane, benzotriazole, benzimidazole, Indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, mercaptopyrimidine, 1,1-dimethylurea, 1,3-dimethylurea, thiourea compound and the like. Functional silane coupling agents are preferred as adhesion promoters.
The amount of adhesion promoter used is preferably 10 parts by weight or less, more preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the total solid content.

In the film-forming composition of the present invention, a pore forming factor can be used within the range allowed by the mechanical strength of the film to make the film porous and to achieve a low dielectric constant.
There are no particular limitations on the pore-forming factor as an additive that serves as a pore-forming agent, but a nonmetallic compound is preferably used, and is soluble in a solvent used in a film-forming coating solution. It is necessary to satisfy the compatibility with the coalescence at the same time.
Further, the boiling point or decomposition temperature of the pore-forming agent is preferably 100 to 500 ° C, more preferably 200 to 450 ° C, and particularly preferably 250 to 400 ° C.
The molecular weight is preferably 200 to 50,000, more preferably 300 to 10,000, and particularly preferably 400 to 5,000.
The addition amount is preferably 0.5 to 75% by weight, more preferably 0.5 to 30% by weight, and particularly preferably 1 to 20% by weight with respect to the polymer forming the film.
The polymer may contain a decomposable group as a pore-forming factor, and the decomposition temperature is preferably 100 to 500 ° C, more preferably 200 to 450 ° C, and particularly preferably 250 to 400 ° C. It is. The content of the decomposable group is preferably 0.5 to 75 mol%, more preferably 0.5 to 30 mol%, and particularly preferably 1 to 20 mol% with respect to the polymer forming the film.

(film)
The film of the present invention is a film obtained by using the film forming composition of the present invention, and can be suitably used as an insulating film.
The method for producing the film of the present invention is not particularly limited, but the step of preparing the film forming composition of the present invention, the step of coating the film forming composition of the present invention into a film, and the coating It is preferable to include a step of heating the film.

A film obtained using the film forming composition of the present invention is obtained by applying the film forming composition to a substrate by any method such as spin coating, roller coating, dip coating, or scanning, and then using a solvent. Can be formed by heat treatment. As a method of applying to the substrate, a spin coating method or a scanning method is preferable. Particularly preferred is the spin coating method. For spin coating, commercially available equipment can be used. For example, a clean truck series (manufactured by Tokyo Electron Co., Ltd.), D-spin series (manufactured by Dainippon Screen Mfg. Co., Ltd.), SS series or CS series (manufactured by Tokyo Ohka Kogyo Co., Ltd.) can be preferably used. The spin coating conditions may be any rotational speed, but from the viewpoint of in-plane uniformity of the film, a rotational speed of about 1,300 rpm is preferable for a 300 mm silicon substrate.
In addition, the composition solution discharge method may be either dynamic discharge in which the composition solution is discharged onto a rotating substrate or static discharge in which the composition solution is discharged onto a stationary substrate. From the viewpoint of uniformity, dynamic ejection is preferable. In addition, from the viewpoint of suppressing the consumption of the composition, it is also possible to use a method in which only the main solvent of the composition is preliminarily discharged onto the substrate to form a liquid film, and then the composition is discharged from there. it can. The spin coating time is not particularly limited, but is preferably within 180 seconds from the viewpoint of throughput. Further, from the viewpoint of transporting the substrate, it is also preferable to perform processing (edge rinse, back rinse) so as not to leave the film at the edge portion of the substrate.
The method of heat treatment is not particularly limited, but it is possible to apply commonly used hot plate heating, heating method using a furnace, light irradiation heating using a xenon lamp by RTP (Rapid Thermal Processor), etc. Can do. A heating method using hot plate heating or furnace is preferable. Commercially available equipment can be preferably used as the hot plate, and the clean track series (manufactured by Tokyo Electron Ltd.), D-Spin series (manufactured by Dainippon Screen Mfg. Co., Ltd.), SS series or CS series (Tokyo Ohka Kogyo Co., Ltd.) )) And the like can be preferably used. As the furnace, α series (manufactured by Tokyo Electron Ltd.) and the like can be preferably used.

When forming a film using the film-forming composition of the present invention, it is preferable to use a coating solvent.
The coating solvent that can be used in the present invention is not particularly limited. For example, alcohols such as methanol, ethanol, 2-propanol, 1-butanol, 2-ethoxymethanol, 3-methoxypropanol, and 1-methoxy-2-propanol are used. Solvents, acetone, acetylacetone, methyl ethyl ketone, methyl isobutyl ketone, 2-pentanone, 3-pentanone, 2-heptanone, 3-heptanone, cyclopentanone, cyclohexanone and other ketone solvents, ethyl acetate, propyl acetate, butyl acetate, acetic acid Isobutyl, pentyl acetate, ethyl propionate, propyl propionate, butyl propionate, isobutyl propionate, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, γ-butyrolactone, etc. Stealth solvents, ether solvents such as diisopropyl ether, dibutyl ether, ethylpropyl ether, anisole, phenetol, veratrol, aromatic hydrocarbon solvents such as mesitylene, ethylbenzene, diethylbenzene, propylbenzene, t-butylbenzene, N-methyl Examples include amide solvents such as pyrrolidinone and dimethylacetamide. These may be used alone or in combination of two or more.
More preferred coating solvents are 1-methoxy-2-propanol, propanol, acetylacetone, cyclohexanone, propylene glycol monomethyl ether acetate, butyl acetate, methyl lactate, ethyl lactate, γ-butyrolactone, anisole, mesitylene, t-butylbenzene, especially Preferred coating solvents are 1-methoxy-2-propanol, cyclohexanone, propylene glycol monomethyl ether acetate, ethyl lactate, γ-butyrolactone, t-butylbenzene, and anisole.

The film-forming composition of the present invention is particularly preferably cured by heat treatment after coating on a substrate. For example, the polymerization reaction at the time of post-heating of the carbon triple bond remaining in the film formed by the film forming composition can be used. The conditions for this post-heat treatment are preferably 100 to 450 ° C., more preferably 200 to 420 ° C., particularly preferably 350 to 400 ° C., preferably 1 minute to 2 hours, more preferably 10 minutes to 1.5 ° C. Time, particularly preferably in the range of 30 minutes to 1 hour. The post-heating treatment may be performed in several times. Further, this post-heating is particularly preferably performed in a nitrogen atmosphere in order to prevent thermal oxidation by oxygen.
In forming the film of the present invention, the polymerized polymer is heated using at least the compound represented by the formula (1) and / or the compound represented by the formula (1) by heat treatment after coating. The coalescence has high heat resistance by reacting the amide bond in the molecule with COOR by heat to form an imide ring. The formation amount (ratio) of the imide ring in the film of the present invention is preferably 50 to 100%, more preferably 70 to 100% of the structure derived from the compound represented by the formula (1), More preferably, it is 80 to 100%.

Moreover, in this invention, you may make it harden | cure by raise | generating the polymerization reaction of the carbon triple bond which remains in a polymer by irradiating a high energy ray instead of heat processing. Examples of high energy rays include electron beams, ultraviolet rays, and X-rays, but are not particularly limited to these methods.
The energy when an electron beam is used as the high energy beam is preferably 0 to 50 keV, more preferably 0 to 30 keV, and particularly preferably 0 to 20 keV. The total dose of the electron beam is preferably 0 to 5 μC / cm ² , more preferably 0 to ² μC / cm ² , and particularly preferably 0 to 1 μC / cm ² . 0-450 degreeC is preferable, as for the substrate temperature at the time of irradiating an electron beam, 0-400 degreeC is more preferable, and 0-350 degreeC is especially preferable. The pressure is preferably 0 to 133 kPa, more preferably 0 to 60 kPa, and particularly preferably 0 to 20 kPa. From the viewpoint of preventing oxidation of the polymer, it is preferable to use an inert atmosphere such as Ar, He, or nitrogen as the atmosphere around the substrate. Further, a gas such as oxygen, hydrocarbon, or ammonia may be added for the purpose of reaction with plasma, electromagnetic waves, or chemical species generated by interaction with an electron beam. The electron beam irradiation in the present invention may be performed a plurality of times. In this case, the electron beam irradiation conditions need not be the same each time, and may be performed under different conditions each time.
Ultraviolet rays may be used as the high energy rays. The irradiation wavelength region when using ultraviolet rays is preferably 190 to 400 nm, and the output is preferably 0.1 to 2,000 mWcm ⁻² immediately above the substrate. The substrate temperature at the time of ultraviolet irradiation is preferably 250 to 450 ° C, more preferably 250 to 400 ° C, and particularly preferably 250 to 350 ° C. From the viewpoint of preventing oxidation of the polymer, it is preferable to use an inert atmosphere such as Ar, He, or nitrogen as the atmosphere around the substrate. Further, the pressure at that time is preferably 0 to 133 kPa.

The film obtained by using the film forming composition of the present invention can be suitably used as an insulating film, and can be more suitably used as an interlayer insulating film for semiconductors. That is, the insulating film obtained using the film forming composition of the present invention can be suitably used for an electronic device.
For example, when used as an interlayer insulating film for a semiconductor, in the wiring structure, there may be a barrier layer on the side surface of the wiring to prevent metal migration, and CMP (chemical In addition to a cap layer and an interlayer adhesion layer that prevent delamination in mechanical mechanical polishing, there may be an etching stopper layer, etc., and further, the interlayer insulating film layer may be divided into multiple layers with other materials as required. Also good.

  The film obtained using the film forming composition of the present invention can be etched for copper wiring or other purposes. Etching may be either wet etching or dry etching, but dry etching is preferred. For dry etching, either ammonia-based plasma or fluorocarbon-based plasma can be used as appropriate. These plasmas can use not only Ar but also oxygen, or gases such as nitrogen, hydrogen, and helium. In addition, after the etching process, ashing can be performed for the purpose of removing the photoresist or the like used for the processing, and further, cleaning can be performed to remove a residue at the time of ashing.

  The film obtained by using the film forming composition of the present invention can be subjected to CMP to planarize the copper plating portion after the copper wiring processing. As the CMP slurry (chemical solution), commercially available slurries (for example, manufactured by Fujimi Incorporated, manufactured by Rodel Nitta, manufactured by JSR, manufactured by Hitachi Chemical Co., Ltd., etc.) can be used as appropriate. Moreover, as a CMP apparatus, a commercially available apparatus (Applied Materials Co., Ltd., Ebara Manufacturing Co., Ltd. etc.) can be used suitably. Further, cleaning can be performed to remove slurry residues after CMP.

The film obtained using the film forming composition of the present invention can be used for various purposes. For example, it is suitable as an insulating film in electronic devices such as semiconductor devices such as LSI, system LSI, DRAM, SDRAM, RDRAM, and D-RDRAM, and multi-chip module multilayer wiring boards. Interlayer insulating film for semiconductor, etching stopper film, surface protection In addition to films, buffer coat films, LSI passivation films, alpha ray blocking films, flexographic printing plate cover lay films, overcoat films, flexible copper clad cover coats, solder resist films, liquid crystal alignment films, etc. Can do.
Furthermore, as another application, the film of the present invention can be imparted with conductivity by doping with an electron donor or acceptor and used as a conductive film.

  In addition, as a method for measuring the Young's modulus in the insulating film of the present invention, it is preferable to use MTS Nanoindenter SA2.

  The following examples illustrate the invention and are not intended to limit its scope.

<Synthesis Example 1: Synthesis of Compound (a)>

Under a nitrogen stream, 0.3 parts by weight of 1,4-diaminobenzene and 22 parts by weight of N-methylpyrrolidone (NMP) were placed in a reaction vessel and stirred until uniform. A solution prepared by dissolving 1.0 part by weight of 4-ethynylphthalic anhydride in 8.0 parts by weight of NMP was slowly dropped into the container. After completion of dropping, the mixture was stirred at room temperature for 1 hour. After the reaction, the reaction solution was added dropwise to distilled water. The precipitated component was collected by filtration to obtain 1.1 parts by weight (yield: 87%) of compound (a).
¹ H-NMR (DMSO) δ = 13.2 (br, 2H), 10.35 (s, 2H), 7.56-7.89 (m, 10H), 4.12-4.88 (m, 2H).

<Synthesis Example 2: Synthesis of Compound (b)>

Under a nitrogen stream, 5.2 parts by weight of 4,4′-diaminodiphenyl ether and 67 parts by weight of N-methylpyrrolidone (NMP) were placed in a reaction vessel and stirred until uniform. A solution prepared by dissolving 10.0 parts by weight of 4-ethynylphthalic anhydride in 50.0 parts by weight of NMP was slowly added dropwise to the container. After completion of dropping, the mixture was stirred at room temperature for 1 hour. After the reaction, the reaction solution was added dropwise to distilled water. The precipitated component was collected by filtration to obtain 10.2 parts by weight (yield: 87%) of compound (b).
¹ H-NMR (DMSO) δ = 13.2 (br, 2H), 10.39 (s, 2H), 7.57-7.90 (m, 10H), 6.99 (d, 4H), 4.04-4.83 (m, 2H).

<Synthesis Example 3: Synthesis of Compound (c)>
The following compound (c) was synthesized in the same manner as in Synthesis Example 2 except that 4,4′-diaminodiphenyl ether was replaced with 1,3-diaminobenzene.

<Synthesis Example 4: Synthesis of Compound (d)>
The following compound (d) was synthesized in the same manner as in Synthesis Example 2 except that 4,4′-diaminodiphenyl ether was replaced with 1,5-diaminonaphthalene.

<Synthesis Example 5: Synthesis of Compound (e)>
The following compound (e) was synthesized in the same manner as in Synthesis Example 2 except that 4,4′-diaminodiphenyl ether was replaced with 3,4′-diaminodiphenyl ether.

<Synthesis Example 6: Synthesis of Compound (f)>
The following compound (f) was synthesized in the same manner as in Synthesis Example 2 except that 4,4′-diaminodiphenyl ether was replaced with 1,4-bis (4-aminophenoxy) benzene.

<Synthesis Example 7: Synthesis of Compound (g)>
The following compound (g) was synthesized in the same manner as in Synthesis Example 2 except that 4,4′-diaminodiphenyl ether was replaced with 1,3-bis (3-aminophenoxy) benzene.

<Synthesis Example 8: Synthesis of Compound (h)>
The following compound (h) was synthesized in the same manner as in Synthesis Example 2 except that 4,4′-diaminodiphenyl ether was replaced with 2,2-bis [4- (4-aminophenoxy) phenyl] propane.

<Synthesis Example 9: Synthesis of Compound (i)>
The following compound (i) was synthesized in the same manner as in Synthesis Example 2 except that 4,4′-diaminodiphenyl ether was replaced with 4,4′-bis (4-aminophenoxy) biphenyl.

  The compound produced by the above synthesis method is not a single compound but a mixture of three isomers having different ethynyl group substitution positions. The yield is also a value including all three isomers. The isomers in the case of compound (a) are shown below.

<Synthesis Example 10: Synthesis of Compound (j)>

0.2 part by weight of compound (a) and 3 parts by weight of N-methylpyrrolidone (NMP) were placed in a reaction vessel and stirred until uniform. To the vessel, 0.18 part by weight of triethylamine was added and stirred at 50 ° C. for 30 minutes. Thereafter, 0.95 parts by weight of 1-iododecane was added and stirred at 50 ° C. for 3 hours. After the reaction, the reaction solution was added dropwise to distilled water. The precipitated component was collected by filtration and washed with n-hexane to obtain 0.1 part by weight (yield: 31%) of compound (j).
¹ H-NMR (DMSO) δ = 10.42-10.66 (m, 2H), 7.61-7.99 (m, 10H), 4.43-4.53 (m, 2H), 4.12 (m, 4H), 0.83-1.50 (m, 38H ).

<Synthesis Example 11: Synthesis of Compound (k)>

0.2 part by weight of compound (d) and 3 parts by weight of N-methylpyrrolidone (NMP) were placed in a reaction vessel and stirred until uniform. To the container, 0.16 part by weight of triethylamine was added and stirred at 50 ° C. for 30 minutes. Thereafter, 0.86 parts by weight of 1-iododecane was added and stirred at 50 ° C. for 3 hours. After the reaction, the reaction solution was added dropwise to distilled water. The precipitated component was collected by filtration and washed with n-hexane to obtain 0.13 parts by weight (yield: 42%) of compound (k).
¹ H-NMR (DMSO) δ = 10.51 (s, 2H), 7.56-8.10 (m, 12H), 4.44-4.55 (m, 2H), 4.19 (m, 4H), 0.82-1.58 (m, 38H).

<Synthesis Example 12: Synthesis of Polymer (L)>

10 parts by weight of compound (b) and 90 parts by weight of t-butylbenzene were placed in a reaction vessel and heated to an internal temperature of 120 ° C. with stirring under a nitrogen stream. Next, a solution obtained by dissolving 2.2 parts by weight of dicumyl peroxide (Park Mill D, manufactured by Nippon Oil & Fats Co., Ltd.) in 1.9 parts by weight of diphenyl ether is maintained while maintaining the internal temperature of the reaction solution at 120 ° C. to 130 ° C. The solution was added dropwise to the reaction solution over 1 hour, and heated and stirred as it was for 1 hour.
After the reaction, the reaction solution was cooled to 50 ° C., added to 314 parts by weight of 2-propanol, and the precipitated solid was filtered and washed with 2-propanol. The obtained polymer was dissolved in 35.6 parts by weight of tetrahydrofuran (THF), added to 316 parts by weight of methanol, and purified by reprecipitation. After vacuum drying, 3.1 parts by weight of polymer (L) having a weight average molecular weight of about 5.0 × 10 ³ was obtained.

  In addition, the structure of the polymer (L) shown above is only an example, and not all of the polymers have this structure.

Example 1
1,3,5-triethynyladamantane was synthesized according to the synthesis method described in J. Polym. Sci. PART A Polym. Chem., Vol. 30, page 1747 (1992).
Next, 10 parts by weight of 1,3,5-triethynyladamantane and 56 parts by weight of t-butylbenzene are placed in a reaction vessel and heated to an internal temperature of 120 ° C. with stirring under a nitrogen stream. , 5-triethynyladamantane was completely dissolved. Next, a solution obtained by dissolving 2.2 parts by weight of dicumyl peroxide (Park Mill D, manufactured by Nippon Oil & Fats Co., Ltd.) in 1.9 parts by weight of diphenyl ether is maintained while maintaining the internal temperature of the reaction solution at 120 ° C. to 130 ° C. The solution was added dropwise to the reaction solution over 1 hour.
After the reaction, the reaction solution was cooled to 50 ° C., added to 314 parts by weight of 2-propanol, and the precipitated solid was filtered and washed with 2-propanol. The obtained polymer was dissolved in 35.6 parts by weight of tetrahydrofuran (THF), added to 316 parts by weight of methanol, and purified by reprecipitation. After vacuum drying, 4.2 parts by weight of polymer (1) having a weight average molecular weight of about 6.0 × 10 ⁴ was obtained.

The polymer (1) and the compounds (a) to (k) obtained in Synthesis Examples 1 to 11 or the polymer (L) obtained in Synthesis Example 12 were added to prepare 1.0 parts by weight, It was completely dissolved in 9.0 parts by weight of cyclohexanone to prepare a coating solution. This solution was filtered through a tetrafluoroethylene filter having a pore size of 0.1 μm, spin-coated on a silicon wafer, this coating film was heated on a hot plate at 250 ° C. for 60 seconds under a nitrogen stream, and further replaced with nitrogen. As a result of baking in an oven at 400 ° C. for 60 minutes, a uniform film having a thickness of 0.5 μm and no defects was obtained.
The relative dielectric constant (k value) of the film (measurement temperature: 25 ° C., the same applies hereinafter) was calculated from the capacitance value at 1 MHz using a mercury probe manufactured by Four Dimensions and an HP4285ALCR meter manufactured by Yokogawa Hewlett-Packard. The appearance of the obtained insulating film was observed with a pocket micro loupe (50 times) manufactured by Peak Co., but no cracks were observed on the coating film surface. The Young's modulus was measured using Nano Indenter SA2 manufactured by MTS.

(Example 2)
Next, 10 parts by weight of 1,3,5-trivinyladamantane and 56 parts by weight of t-butylbenzene were placed in a reaction vessel and heated to an internal temperature of 120 ° C. with stirring under a nitrogen stream. 5-Trivinyladamantane was completely dissolved. Next, a solution obtained by dissolving 2.2 parts by weight of dicumyl peroxide (Park Mill D, manufactured by Nippon Oil & Fats Co., Ltd.) in 1.9 parts by weight of diphenyl ether is maintained while maintaining the internal temperature of the reaction solution at 120 ° C. to 130 ° C. The solution was added dropwise to the reaction solution over 1 hour.
After the reaction, the reaction solution was cooled to 50 ° C., added to 314 parts by weight of 2-propanol, and the precipitated solid was filtered and washed with 2-propanol. The obtained polymer was dissolved in 35.6 parts by weight of THF, added to 316 parts by weight of methanol, and purified by reprecipitation. After vacuum drying, 4.0 parts by weight of polymer (2) having a weight average molecular weight of about 6.0 × 10 ⁴ was obtained.

The polymer (2) and the compounds (a) to (k) obtained in Synthesis Examples 1 to 11 or the polymer (L) obtained in Synthesis Example 12 were added to prepare 1.0 parts by weight, It was completely dissolved in 9.0 parts by weight of cyclohexanone to prepare a coating solution. This solution was filtered through a tetrafluoroethylene filter having a pore size of 0.1 μm, spin-coated on a silicon wafer, this coating film was heated on a hot plate at 250 ° C. for 60 seconds under a nitrogen stream, and further replaced with nitrogen. As a result of baking in an oven at 400 ° C. for 60 minutes, a uniform film having a thickness of 0.5 μm and no defects was obtained.
The relative dielectric constant of the film (measurement temperature: 25 ° C., the same applies hereinafter) was calculated from the capacitance value at 1 MHz using a mercury probe manufactured by Four Dimensions and an HP4285ALCR meter manufactured by Yokogawa Hewlett-Packard. The appearance of the obtained insulating film was observed with a pocket micro loupe (50 times) manufactured by Peak Co., but no cracks were observed on the coating film surface. Further, the Young's modulus was measured using a nano indenter SA2 manufactured by MTS.

(Comparative Example 1)
Only the polymer (1) of Example 1 was prepared at 1.0 part by weight. This coating solution was filtered through a tetrafluoroethylene filter having a pore size of 0.1 μm, spin-coated on a silicon wafer, this coating film was heated on a hot plate at 250 ° C. for 60 seconds under a nitrogen stream, As a result of baking for 60 minutes in a substituted 400 ° C. oven, a uniform film having a thickness of 0.5 μm and no defects was obtained.
The relative dielectric constant of the film (measurement temperature: 25 ° C., and so on) was calculated from the capacitance value at 1 MHz using a mercury probe manufactured by Four Dimensions and an HP4285ALCR meter manufactured by Yokogawa Hewlett-Packard, and found to be 2.65. there were. The appearance of the obtained insulating film was observed with a pocket micro loupe (50 times) manufactured by Peak Co., but no cracks were observed on the coating film surface. Moreover, it was 5.0 GPa when the Young's modulus was measured using Nano Indenter SA2 from MTS.

(Comparative Example 2)
A coating solution was prepared with 1.0 part by weight of the polymer (2) of Example 1 only. This coating solution was filtered through a tetrafluoroethylene filter having a pore size of 0.1 μm, spin-coated on a silicon wafer, this coating film was heated on a hot plate at 250 ° C. for 60 seconds under a nitrogen stream, As a result of baking for 60 minutes in a substituted 400 ° C. oven, a uniform film having a thickness of 0.5 μm and no defects was obtained.
The relative dielectric constant of the film (measurement temperature: 25 ° C., and so on) was calculated from the capacitance value at 1 MHz using a mercury probe manufactured by Four Dimensions and a HP4285ALCR meter manufactured by Yokogawa Hewlett-Packard Co., and found to be 2.63. there were. The appearance of the obtained insulating film was observed with a pocket micro loupe (50 times) manufactured by Peak Co., but no cracks were observed on the coating film surface. Moreover, it was 5.0 GPa when the Young's modulus was measured using Nano Indenter SA2 from MTS.

<Comparison of increase in dielectric constant with time, mechanical strength and heat resistance>
The increase in dielectric constant with time was measured by measuring the k value after one week at 25 ° C. in the atmosphere. Further, the difference (Δk) between the initial k value and the k value measured after one week had elapsed.
In addition, k value was computed from the capacity | capacitance value in 1 MHz using the Mercury prober made from Four Dimensions, and HP4285ALCR meter made from Yokogawa Hewlett-Packard.
The mechanical strength (Young's modulus) was measured using MTS Nanoindenter SA2.
The heat resistance was evaluated by heating in air at 400 ° C. for 30 seconds and measuring the change in weight.

  The evaluation results of the films obtained in Examples 1 and 2 and Comparative Examples 1 and 2 are shown below.

  A film (insulating film) formed using the film-forming composition of the present invention has excellent heat resistance and mechanical strength, has a low dielectric constant, and exhibits excellent temporal stability with respect to the dielectric constant. I understand.

Claims (11)

A film-forming composition comprising a polymer obtained by polymerizing at least a compound represented by the following formula (1) and / or a compound represented by the following formula (1).

(In Formula (1), A ¹ represents a divalent to tetravalent organic group, A ² represents an alkenyl group or an alkynyl group, Ar represents a (2 + a1) valent aryl group, and R represents a hydrogen atom or a carbon number. A 1 represents an integer of 1-4, a2 represents an integer of 2-4.   The film forming composition according to claim 1, which is used for forming an insulating film.   The film-forming composition according to claim 1 or 2, comprising a compound having a cage structure and / or a polymer having a cage structure.   The film forming composition according to any one of claims 1 to 3, comprising a polymer having a cage structure.   The film-forming composition according to claim 4, wherein the polymer having a cage structure is obtained by polymerizing a monomer having a cage structure in the presence of a radical initiator or a transition metal catalyst.   The film-forming composition according to claim 5, wherein the monomer having a cage structure has a polymerizable carbon-carbon double bond and / or carbon-carbon triple bond.   The film forming composition according to any one of claims 3 to 6, wherein the cage structure is a structure selected from the group consisting of adamantane, biadamantane, diamantane, triamantane, and tetramantane. The film forming composition according to claim 5 or 6, wherein the monomer having a cage structure is a monomer selected from the group consisting of monomers represented by the following formulas (2) to (7).

(In the formulas (2) to (7), X _{1 to} X ₈ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a silyl group, an acyl group, an alkoxycarbonyl group or a carbamoyl group. , Y _{1 to} Y ₈ each independently represents a halogen atom, an alkyl group, an aryl group or a silyl group, m ₁ and m ₅ represent an integer of ₁ to 16, and n ₁ and n ₅ represent an integer of 0 to 15 M ₂ , m ₃ , m ₆ and m ₇ each independently represent an integer of 1 to 15, n ₂ , n ₃ , n ₆ and n ₇ represent an integer of 0 to 14, m ₄ , m ₈ represents an integer of 1 to 20, and n ₄ and n ₈ represent an integer of 0 to 19.)   The film | membrane obtained using the composition for film formation as described in any one of Claims 1-8.   The film according to claim 9 which is an insulating film.   An electronic device having the film according to claim 9.