JP2008195862A - Composition for forming insulation film, and silica based film and method of forming the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for forming an insulating film which can be suitably used in semiconductor devices expecting high integration and multilayering and the like. <P>SOLUTION: The composition for forming an insulating film comprises a first hydrolysis condensate obtained by the hydrolysis condensation of a 50-100 mol% at least one silane compound selected from the group consisting of specific tetraalkoxy silane compounds and specific silane compounds having oxygen, a phenylene group or a 1-6C alkylene group in the molecule and 0-50 mol% another silane compound, a second hydrolysis condensate obtained by the hydrolysis condensation of more than 50 mol% one specific silane compound having 2 ot 3 alkoxy groups in the molecule and less than 50 mol% another silane compound, and an organic solvent, and the first hydrolysis condensate and the second hydrolysis condensate have a weight average molecular weight of 700-20,000, respectively. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a composition for forming an insulating film, a silica-based film, and a method for forming the same.

Conventionally, a silica (SiO ₂ ) film formed by a vacuum process such as a CVD method is often used as an interlayer insulating film in a semiconductor element or the like. In recent years, for the purpose of forming a more uniform interlayer insulating film, a coating type insulating film called a SOG (Spin on Glass) film containing a hydrolysis product of tetraalkoxylane as a main component has been used. It has become.

  In general, an organic silica sol composition for a low relative dielectric constant insulating film used for a semiconductor device is subjected to thermal mechanical curing in consideration of the yield in a process in which mechanical stresses such as CMP (Chemical Mechanical Polishing) and packaging occur. The composition of the organic silica sol is controlled so that the obtained organic silica film exhibits a high elastic modulus (for example, US Pat. No. 6,495,264). Specifically, by increasing the tetrafunctional silane compound in the organic silica sol or the silane compound having a larger number of hydrolyzable substituents to usually 40 mol% or more, the absolute crosslinking density in the silica film can be increased. We are trying to improve. By increasing the component ratio of these silane compounds, the crosslinking density increases, and a film having a high elastic modulus and hardness can be obtained. However, the insulating film thus obtained tends to have a high relative dielectric constant due to damage accompanying chemical changes caused by processing processes such as etching and ashing generally used in the manufacture of semiconductor devices. Further, in the cleaning process after ashing, a chemical solution such as dilute hydrofluoric acid is generally used, and it is said that this treatment often causes damage accompanied by a chemical change. Accordingly, there is a need for an interlayer insulating film that not only has high mechanical properties but also has sufficient resistance to manufacturing processes.

On the other hand, as a method for manufacturing a semiconductor laminated structure, a method has been proposed in which metal wiring such as aluminum or tungsten is first constructed, and thereafter an insulating film is provided by applying an interlayer insulating film. However, in recent years, with high integration, the pitch between wirings has been narrowed to about several to several tens of nanometers, and it has become increasingly difficult to embed an insulating film in the gap without a defect. Therefore, embeddability in gaps with a narrow pitch of several to several tens of nanometers is an important factor in developing a coating type interlayer insulating film.
US Pat. No. 6,495,264

  The object of the present invention can be suitably used in semiconductor elements and the like that are desired to be highly integrated and multi-layered, have low hygroscopicity, low dielectric constant, excellent mechanical strength, and narrow pitch. An object of the present invention is to provide a composition for forming an insulating film that can be used for forming an insulating film that is excellent in embedding in the gap.

  Another object of the present invention is to provide a silica-based film having a low relative dielectric constant and excellent mechanical strength, and a method for forming the same.

The composition for forming an insulating film according to one embodiment of the present invention includes:
50-100 mol% of at least one silane compound selected from the group of compounds represented by the following general formula (1) and the following general formula (2), and 0-50 mol of other silane compounds A first hydrolytic condensate obtained by hydrolytic condensation of
A second hydrolysis-condensation product obtained by hydrolytic condensation of more than 50 mol% of at least one silane compound represented by the following general formula (3) and less than 50 mol% of another silane compound;
An organic solvent,
Including
The composition for insulating film formation whose weight average molecular weights of said 1st hydrolysis-condensation product and said 2nd hydrolysis-condensation product are 700 or more and 20,000 or less.
Si (OR ¹ ) ₄ (1)
(In the formula, R ¹ represents a monovalent organic group.)
_{^{R 2 a (R 3 O)}} 3-a Si- (R 6) c -Si (OR 4) 3-b R 5 b ··· (2)
(Wherein R ^{2 to} R ⁵ independently represent a monovalent organic group, a and b each independently represents a number of 0 to 1, and R ⁶ represents an oxygen atom, a phenylene group or — (CH ₂ ) represents a group represented by _m- (where m is an integer of 1 to 6), and c represents 0 or 1.)
R ⁷ _d Si (OR ⁸ ) _4-d (3)
(In formula, R < ⁷ > -R < ⁸ > represents a monovalent organic group independently, d shows the number of 1-2.)
In the composition for forming an insulating film, the other silane compound for obtaining the first hydrolysis condensate may be a compound represented by the general formula (3).

  In the composition for forming an insulating film, the other silane compound for obtaining the second hydrolysis-condensation product may be a compound represented by the general formula (1).

  In the composition for forming an insulating film, the other silane compound may be a compound represented by the general formula (3).

  In the insulating film forming composition, a ratio of the first hydrolysis condensate to the total amount of the first hydrolysis condensate and the second hydrolysis condensate may be 5 to 95% by mass. .

  The composition for forming an insulating film may further contain an organic polymer as a film hollow hole forming agent.

  The method for forming a silica-based film according to one embodiment of the present invention includes a step of applying the insulating film forming composition to a substrate to form a coating film, and a step of applying a curing treatment to the coating film.

  The silica film according to one embodiment of the present invention is obtained by the method for forming a silica film.

  According to the composition for forming an insulating film, the molecular weight of the second hydrolysis-condensation product is higher than the molecular weight of the first hydrolysis-condensation product, including the first and second hydrolysis-condensation products and the organic solvent. Thus, an insulating film having excellent mechanical strength, low hygroscopicity, and low relative dielectric constant can be formed.

  The silica-based film has a low relative dielectric constant, excellent mechanical strength, and low hygroscopicity.

  Hereinafter, a composition for forming an insulating film according to an embodiment of the present invention, a silica-based film, and a method for forming the same will be described in detail.

1. Composition for Insulating Film Formation and Production Thereof A composition for forming an insulating film according to an embodiment of the present invention includes a compound represented by the following general formula (1) (hereinafter also referred to as “compound 1”) and the following general formula. 50 to 100 mol% of at least one silane compound (hereinafter also referred to as “component (A)”) selected from the group of compounds represented by formula (2) (hereinafter also referred to as “compound 2”). And a first hydrolytic condensate obtained by hydrolytic condensation of 0 to 50 mol% of another silane compound (hereinafter also referred to as “component (B)”), and the following general formula (3): More than 50 mol% of at least one silane compound (hereinafter also referred to as “component (C)”) and less than 50 mol% of other silane compounds (hereinafter also referred to as “component (D)”). A second hydrolysis-condensation product obtained by hydrolysis-condensation and an organic solvent .
Si (OR ¹ ) ₄ (1)
(In the formula, R ¹ represents a monovalent organic group.)
_{^{R 2 a (R 3 O)}} 3-a Si- (R 6) c -Si (OR 4) 3-b R 5 b ··· (2)
(Wherein R ^{2 to} R ⁵ independently represent a monovalent organic group, a and b each independently represents a number of 0 to 1, and R ⁶ represents an oxygen atom, a phenylene group or — (CH ₂ ) represents a group represented by _m- (where m is an integer of 1 to 6), and c represents 0 or 1.)
R ⁷ _d Si (OR ⁸ ) _4-d (3)
(In formula, R < ⁷ > -R < ⁸ > represents a monovalent organic group independently, d shows the number of 1-2.)
The molecular weight of the second hydrolysis condensate is preferably 0.1 to 10 times the molecular weight of the first hydrolysis condensate. Moreover, it is preferable that the ratio of the 1st hydrolysis-condensation product with respect to the total amount (100 mass%) of a 1st hydrolysis-condensation product and a 2nd hydrolysis-condensation product is 5-95 mass%. % Is more preferable.

  When the ratio is less than 5% by mass, the mechanical strength of the formed insulating film may be inferior, or when it exceeds 95% by mass, the hygroscopicity of the formed insulating film may be increased.

  Hereinafter, each component used in order to manufacture the composition for insulating film formation concerning this embodiment is demonstrated.

1.1. 1st hydrolysis-condensate In the composition for insulating film formation which concerns on this embodiment, (A) component and (B) component used in order to manufacture the 1st hydrolysis-condensation product are (A) component and When the sum total of (B) component shall be 100 mol%, (A) component is 50-100 mol%, it is preferable that it is 60-100 mol%, and it is more preferable that it is 70-100 mol%. When the component (A) is less than 50 mol%, the mechanical strength of the formed insulating film may be inferior.

  As compound 1 and compound 2 used as component (A), compound 1 or compound 2 may be used alone, or both compound 1 and compound 2 may be used.

  The weight average molecular weight of the first hydrolysis-condensation product is preferably 700 to 20,000, and more preferably 1,000 to 15,000. When the weight average molecular weight of the first hydrolysis-condensation product is not in the range of 700 to 20,000, the hygroscopicity of the formed insulating film is increased, or the embeddability in the narrow pitch gap is decreased. There is.

1.1.1. (A) Component Compound 1 and Compound 2 that can be used as the component (A) will be described.

1.1.1.1. Compound 1
In the general formula (1), examples of the monovalent organic group represented by R ¹ include an alkyl group, an alkenyl group, an aryl group, an allyl group, and a glycidyl group. Among these, the monovalent organic group represented by R ¹ is preferably an alkyl group or a phenyl group.

  Here, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and the like. Preferably, the alkyl group has 1 to 5 carbon atoms, and these alkyl groups may be linear or branched. Further, a hydrogen atom may be substituted with a fluorine atom or the like. Examples of the aryl group include a phenyl group, a naphthyl group, a methylphenyl group, an ethylphenyl group, a chlorophenyl group, a bromophenyl group, and a fluorophenyl group. Examples of the alkenyl group include a vinyl group, a propenyl group, a 3-butenyl group, a 3-pentenyl group, and a 3-hexenyl group.

  Specific examples of the compound 1 include, for example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxy. Silane, tetraphenoxysilane and the like can be mentioned, and particularly preferred compounds include tetramethoxysilane and tetraethoxysilane. Compound 1 may be used alone or in combination of two or more.

1.1.1-2. Compound 2
In the general formula (2), examples of R ^{2 to} R ⁵ include the same groups as those exemplified as R ^{1 in the} general formula (1).

  In the general formula (2), the compound 2 having c = 0 includes hexamethoxydisilane, hexaethoxydisilane, hexaphenoxydisilane, 1,1,1,2,2-pentamethoxy-2-methyldisilane, 1,1, 1,2,2-pentaethoxy-2-methyldisilane, 1,1,1,2,2-pentaphenoxy-2-methyldisilane, 1,1,1,2,2-pentamethoxy-2-ethyldisilane, 1,1,1,2,2-pentaethoxy-2-ethyldisilane, 1,1,1,2,2-pentaphenoxy-2-ethyldisilane, 1,1,1,2,2-pentamethoxy-2 -Phenyldisilane, 1,1,1,2,2-pentaethoxy-2-phenyldisilane, 1,1,1,2,2-pentaphenoxy-2-phenyldisilane, 1,1,2,2-tetrameth Si-1,2-dimethyldisilane, 1,1,2,2-tetraethoxy-1,2-dimethyldisilane, 1,1,2,2-tetraphenoxy-1,2-dimethyldisilane, 1,1,2 , 2-tetramethoxy-1,2-diethyldisilane, 1,1,2,2-tetraethoxy-1,2-diethyldisilane, 1,1,2,2-tetraphenoxy-1,2-diethyldisilane, , 1,2,2-tetramethoxy-1,2-diphenyldisilane, 1,1,2,2-tetraethoxy-1,2-diphenyldisilane, 1,1,2,2-tetraphenoxy-1,2- Diphenyldisilane, 1,1,2-trimethoxy-1,2,2-trimethyldisilane, 1,1,2-triethoxy-1,2,2-trimethyldisilane, 1,1,2-triphenoxy-1,2, 2-G Methyldisilane, 1,1,2-trimethoxy-1,2,2-triethyldisilane, 1,1,2-triethoxy-1,2,2-triethyldisilane, 1,1,2-triphenoxy-1,2, 2-triethyldisilane, 1,1,2-trimethoxy-1,2,2-triphenyldisilane, 1,1,2-triethoxy-1,2,2-triphenyldisilane, 1,1,2-triphenoxy- 1,2,2-triphenyldisilane, 1,2-dimethoxy-1,1,2,2-tetramethyldisilane, 1,2-diethoxy-1,1,2,2-tetramethyldisilane, 1,2- Diphenoxy-1,1,2,2-tetramethyldisilane, 1,2-dimethoxy-1,1,2,2-tetraethyldisilane, 1,2-diethoxy-1,1,2,2-tetraethyldisilane, 1,2-diphenoxy-1,1,2,2-tetraethyldisilane, 1,2-dimethoxy-1,1,2,2-tetraphenyldisilane, 1,2-diethoxy-1,1,2,2-tetra Examples thereof include phenyldisilane, 1,2-diphenoxy-1,1,2,2-tetraphenyldisilane, and the like.

  Of these, hexamethoxydisilane, hexaethoxydisilane, 1,1,2,2-tetramethoxy-1,2-dimethyldisilane, 1,1,2,2-tetraethoxy-1,2-dimethyldisilane, 1, 1,2,2-tetramethoxy-1,2-diphenyldisilane, 1,2-dimethoxy-1,1,2,2-tetramethyldisilane, 1,2-diethoxy-1,1,2,2-tetramethyl Preferred examples include disilane, 1,2-dimethoxy-1,1,2,2-tetraphenyldisilane, 1,2-diethoxy-1,1,2,2-tetraphenyldisilane, and the like.

  In addition, as the compound 2 in which c = 1 in the general formula (2), bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, bis (tri-n-propoxysilyl) methane, bis (tri-iso) -Propoxysilyl) methane, bis (tri-n-butoxysilyl) methane, bis (tri-sec-butoxysilyl) methane, bis (tri-tert-butoxysilyl) methane, 1,2-bis (trimethoxysilyl) ethane 1,2-bis (triethoxysilyl) ethane, 1,2-bis (tri-n-propoxysilyl) ethane, 1,2-bis (tri-iso-propoxysilyl) ethane, 1,2-bis (tri -N-butoxysilyl) ethane, 1,2-bis (tri-sec-butoxysilyl) ethane, 1,2-bis (tri-tert-butoxy) Silyl) ethane, 1- (dimethoxymethylsilyl) -1- (trimethoxysilyl) methane, 1- (diethoxymethylsilyl) -1- (triethoxysilyl) methane, 1- (di-n-propoxymethylsilyl) -1- (tri-n-propoxysilyl) methane, 1- (di-iso-propoxymethylsilyl) -1- (tri-iso-propoxysilyl) methane, 1- (di-n-butoxymethylsilyl) -1 -(Tri-n-butoxysilyl) methane, 1- (di-sec-butoxymethylsilyl) -1- (tri-sec-butoxysilyl) methane, 1- (di-tert-butoxymethylsilyl) -1- ( Tri-tert-butoxysilyl) methane, 1- (dimethoxymethylsilyl) -2- (trimethoxysilyl) ethane, 1- (diethoxymethylsilane) L) -2- (triethoxysilyl) ethane, 1- (di-n-propoxymethylsilyl) -2- (tri-n-propoxysilyl) ethane, 1- (di-iso-propoxymethylsilyl) -2- (Tri-iso-propoxysilyl) ethane, 1- (di-n-butoxymethylsilyl) -2- (tri-n-butoxysilyl) ethane, 1- (di-sec-butoxymethylsilyl) -2- (tri -Sec-butoxysilyl) ethane, 1- (di-tert-butoxymethylsilyl) -2- (tri-tert-butoxysilyl) ethane, bis (dimethoxymethylsilyl) methane, bis (diethoxymethylsilyl) methane, bis (Di-n-propoxymethylsilyl) methane, bis (di-iso-propoxymethylsilyl) methane, bis (di-n-butoxymethyl) Silyl) methane, bis (di-sec-butoxymethylsilyl) methane, bis (di-tert-butoxymethylsilyl) methane, 1,2-bis (dimethoxymethylsilyl) ethane, 1,2-bis (diethoxymethylsilyl) ) Ethane, 1,2-bis (di-n-propoxymethylsilyl) ethane, 1,2-bis (di-iso-propoxymethylsilyl) ethane, 1,2-bis (di-n-butoxymethylsilyl) ethane 1,2-bis (di-sec-butoxymethylsilyl) ethane, 1,2-bis (di-tert-butoxymethylsilyl) ethane, 1,2-bis (trimethoxysilyl) benzene, 1,2-bis (Triethoxysilyl) benzene, 1,2-bis (tri-n-propoxysilyl) benzene, 1,2-bis (tri-iso-propoxysilyl) ) Benzene, 1,2-bis (tri-n-butoxysilyl) benzene, 1,2-bis (tri-sec-butoxysilyl) benzene, 1,2-bis (tri-tert-butoxysilyl) benzene, 1, 3-bis (trimethoxysilyl) benzene, 1,3-bis (triethoxysilyl) benzene, 1,3-bis (tri-n-propoxysilyl) benzene, 1,3-bis (tri-iso-propoxysilyl) Benzene, 1,3-bis (tri-n-butoxysilyl) benzene, 1,3-bis (tri-sec-butoxysilyl) benzene, 1,3-bis (tri-tert-butoxysilyl) benzene, 1,4 -Bis (trimethoxysilyl) benzene, 1,4-bis (triethoxysilyl) benzene, 1,4-bis (tri-n-propoxysilyl) benzene 1,4-bis (tri-iso-propoxysilyl) benzene, 1,4-bis (tri-n-butoxysilyl) benzene, 1,4-bis (tri-sec-butoxysilyl) benzene, 1,4- Bis (tri-tert-butoxysilyl) benzene and the like can be mentioned.

  Of these, bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, 1,2-bis (trimethoxysilyl) ethane, 1,2-bis (triethoxysilyl) ethane, 1- (dimethoxymethylsilyl) ) -1- (trimethoxysilyl) methane, 1- (diethoxymethylsilyl) -1- (triethoxysilyl) methane, 1- (dimethoxymethylsilyl) -2- (trimethoxysilyl) ethane, 1- (di Ethoxymethylsilyl) -2- (triethoxysilyl) ethane, bis (dimethoxymethylsilyl) methane, bis (diethoxymethylsilyl) methane, 1,2-bis (dimethoxymethylsilyl) ethane, 1,2-bis (di Ethoxymethylsilyl) ethane, 1,2-bis (trimethoxysilyl) benzene, 1,2-bis (triethoxy) Silyl) benzene, 1,3-bis (trimethoxysilyl) benzene, 1,3-bis (triethoxysilyl) benzene, 1,4-bis (trimethoxysilyl) benzene, 1,4-bis (triethoxysilyl) Benzene etc. can be mentioned as a preferable example.

  The compound 2 mentioned above may use 1 type (s) or 2 or more types simultaneously.

1.1.2. Component (B) The other silane compound as component (B) is a hydrolyzable silane compound (a silane compound having a group that can be hydrolyzed during hydrolysis condensation), and is represented by the following general formula (3), for example. It is preferably a compound (hereinafter also referred to as “compound 3”).
R ⁷ _d Si (OR ⁸ ) _4-d (3)
(In formula, R < ⁷ > -R < ⁸ > represents a monovalent organic group independently, d shows the number of 1-2.)
In the general formula (3), examples of the monovalent organic group represented by R ⁷ and R ⁸ include the same groups as those exemplified as R ^{1 in the} general formula (1).

  Specific examples of the compound 3 include, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltriisopropoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxysilane, methyltri-tert. -Butoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltriisopropoxysilane, ethyltri-n-butoxysilane, ethyltri-sec-butoxysilane, ethyltri-tert- Butoxysilane, ethyltriphenoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltri-n-propoxysilane, n-propyltriisopro Xysilane, n-propyltri-n-butoxysilane, n-propyltri-sec-butoxysilane, n-propyltri-tert-butoxysilane, n-propyltriphenoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, isopropyl Tri-n-propoxysilane, isopropyltriisopropoxysilane, isopropyltri-n-butoxysilane, isopropyltri-sec-butoxysilane, isopropyltri-tert-butoxysilane, isopropyltriphenoxysilane, n-butyltrimethoxysilane, n -Butyltriethoxysilane, n-butyltri-n-propoxysilane, n-butyltriisopropoxysilane, n-butyltri-n-butoxysilane, n-butyltri-sec- Toxisilane, n-butyltri-tert-butoxysilane, n-butyltriphenoxysilane, sec-butyltrimethoxysilane, sec-butylisotriethoxysilane, sec-butyltri-n-propoxysilane, sec-butyltriisopropoxysilane, sec-butyltri-n-butoxysilane, sec-butyltri-sec-butoxysilane, sec-butyltri-tert-butoxysilane, sec-butyltriphenoxysilane, tert-butyltrimethoxysilane, tert-butyltriethoxysilane, tert- Butyl-n-propoxysilane, tert-butyltriisopropoxysilane, tert-butyltri-n-butoxysilane, tert-butyltri-sec-butoxysilane, tert-butyl Rutri-tert-butoxysilane, tert-butyltriphenoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltriisopropoxysilane, phenyltri-n-butoxysilane, phenyltri-sec -Butoxysilane, phenyltri-tert-butoxysilane, phenyltriphenoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, dimethyldiisopropoxysilane, dimethyldi-n-butoxysilane, dimethyldi-sec- Butoxysilane, dimethyldi-tert-butoxysilane, dimethyldiphenoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldi-n-propo Sisilane, diethyldiisopropoxysilane, diethyldi-n-butoxysilane, diethyldi-sec-butoxysilane, diethyldi-tert-butoxysilane, diethyldiphenoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane Di-n-propyldi-n-propoxysilane, di-n-propyldiisopropoxysilane, di-n-propyldi-n-butoxysilane, di-n-propyldi-sec-butoxysilane, di-n-propyldi- tert-butoxysilane, di-n-propyldi-phenoxysilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, diisopropyldi-n-propoxysilane, diisopropyldiisopropoxysilane, diisopropyldi-n-butoxy Silane, diisopropyldi-sec-butoxysilane, diisopropyldi-tert-butoxysilane, diisopropyldiphenoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-butyldi-n-propoxysilane , Di-n-butyldiisopropoxysilane, di-n-butyldi-n-butoxysilane, di-n-butyldi-sec-butoxysilane, di-n-butyldi-tert-butoxysilane, di-n-butyldi- Phenoxysilane, di-sec-butyldimethoxysilane, di-sec-butyldiethoxysilane, di-sec-butyldi-n-propoxysilane, di-sec-butyldiisopropoxysilane, di-sec-butyldi-n-butoxy Silane, di-sec-butyl di-sec-butoxy Sisilane, di-sec-butyldi-tert-butoxysilane, di-sec-butyldi-phenoxysilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, di-tert-butyldi-n-propoxysilane, Di-tert-butyldiisopropoxysilane, di-tert-butyldi-n-butoxysilane, di-tert-butyldi-sec-butoxysilane, di-tert-butyldi-tert-butoxysilane, di-tert-butyldi-phenoxy Silane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldi-n-propoxysilane, diphenyldiisopropoxysilane, diphenyldi-n-butoxysilane, diphenyldi-sec-butoxysilane, diphenyldi-ter - butoxysilane include diphenyl phenoxy silanes. These may be used alone or in combination of two or more.

  More preferable compounds as the compound 3 are methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxy. Silane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane and the like. These may be used alone or in combination of two or more.

  The compound 3 is more preferably a compound (trifunctional silane compound) in which d is 1 in the general formula (3) in that a film having high mechanical strength can be obtained.

1.2. Second hydrolysis condensate In the insulating film forming composition according to the present embodiment, the component (C) and the component (D) used for producing the second hydrolysis condensate are the component (C) and When the sum total of (D) component shall be 100 mol%, (C) component is more than 50 mol%, it is preferable that it is 60-100 mol%, and it is more preferable that it is 70-100 mol%. When the component (C) is 50 mol% or less, the dielectric constant of the formed insulating film is increased, and the chemical resistance may be inferior.

  The weight average molecular weight of the second hydrolysis-condensation product is preferably 700 to 20,000, and more preferably 1,000 to 15,000. When the weight average molecular weight of the first hydrolysis-condensation product is not in the range of 700 to 20,000, the hygroscopicity of the formed insulating film may be increased, or the embeddability in a narrow pitch gap may be reduced. is there.

  As the component (C), the above-described compound 3 can be used. Moreover, the above-mentioned compound 1 can be used as (D) component.

1.3. Production of first and second hydrolysis condensates 1.3.1. (C) Catalyst (C) A catalyst can be used in producing the first and second hydrolysis-condensation products. (C) The catalyst is preferably at least one compound selected from a basic compound, an acidic compound, and a metal chelate compound.

  For example, when producing the 1st hydrolysis condensate and the 2nd hydrolysis condensate, an acidic compound and a metal chelate compound, or any one can be used as (C) catalyst. In this case, the weight average molecular weights of the first hydrolysis condensate and the second hydrolysis condensate can be easily adjusted to 700 to 20,000.

1.3.1.1-1. Metal chelate compound (C) The metal chelate compound which can be used as a catalyst is represented by the following general formula (4).

R ⁹ _e M (OR ¹⁰ ) _fe (4)
(In the formula, R ⁹ represents a chelating agent, M represents a metal atom, R ¹⁰ represents an alkyl group or an aryl group, f represents a valence of the metal M, and e represents an integer of 1 to f.)
Here, the metal M is preferably at least one metal selected from Group IIIB metals (aluminum, gallium, indium, thallium) and Group IVA metals (titanium, zirconium, hafnium). Titanium, aluminum, zirconium Is more preferable. Examples of the alkyl group or aryl group represented by R ¹⁰ include the alkyl group or aryl group represented by R ¹ in the general formula (1).

  Specific examples of metal chelate compounds include triethoxy mono (acetylacetonato) titanium, tri-n-propoxy mono (acetylacetonato) titanium, triisopropoxy mono (acetylacetonato) titanium, tri-n-butoxy. Mono (acetylacetonato) titanium, tri-sec-butoxy mono (acetylacetonato) titanium, tri-tert-butoxy mono (acetylacetonato) titanium, diethoxybis (acetylacetonato) titanium, di-n -Propoxy bis (acetylacetonato) titanium, diisopropoxy bis (acetylacetonato) titanium, di-n-butoxy bis (acetylacetonato) titanium, di-sec-butoxy bis (acetylacetonato) titanium J-tert-but Si-bis (acetylacetonato) titanium, monoethoxy-tris (acetylacetonato) titanium, mono-n-propoxy-tris (acetylacetonato) titanium, monoisopropoxy-tris (acetylacetonato) titanium, mono-n -Butoxy-tris (acetylacetonato) titanium, mono-sec-butoxy-tris (acetylacetonato) titanium, mono-tert-butoxy-tris (acetylacetonato) titanium, tetrakis (acetylacetonato) titanium, triethoxy mono (Ethyl acetoacetate) titanium, tri-n-propoxy mono (ethyl acetoacetate) titanium, triisopropoxy mono (ethyl acetoacetate) titanium, tri-n-butoxy mono (ethyl acetoacetate) titanium, Re-sec-butoxy mono (ethyl acetoacetate) titanium, tri-tert-butoxy mono (ethyl acetoacetate) titanium, diethoxy bis (ethyl acetoacetate) titanium, di-n-propoxy bis (ethyl acetoacetate) Titanium, diisopropoxy bis (ethyl acetoacetate) titanium, di-n-butoxy bis (ethyl acetoacetate) titanium, di-sec-butoxy bis (ethyl acetoacetate) titanium, di-tert-butoxy bis ( Ethyl acetoacetate) titanium, monoethoxy tris (ethyl acetoacetate) titanium, mono-n-propoxy tris (ethyl acetoacetate) titanium, monoisopropoxy tris (ethyl acetoacetate) titanium, mono-n-butoxy tri Sus (ethyl acetoacetate) titanium, mono-sec-butoxy tris (ethyl acetoacetate) titanium, mono-tert-butoxy tris (ethyl acetoacetate) titanium, tetrakis (ethyl acetoacetate) titanium, mono (acetylacetonate) Titanium chelate compounds such as tris (ethylacetoacetate) titanium, bis (acetylacetonate) bis (ethylacetoacetate) titanium, tris (acetylacetonate) mono (ethylacetoacetate) titanium; triethoxy mono (acetylacetonate) Zirconium, tri-n-propoxy mono (acetylacetonato) zirconium, triisopropoxy mono (acetylacetonato) zirconium, tri-n-butoxy mono (acetylacetonate) Zirconium, tri-sec-butoxy mono (acetylacetonato) zirconium, tri-tert-butoxy mono (acetylacetonato) zirconium, diethoxybis (acetylacetonato) zirconium, di-n-propoxybis (acetylacetate) Nate) zirconium, diisopropoxy bis (acetylacetonato) zirconium, di-n-butoxy bis (acetylacetonato) zirconium, di-sec-butoxy bis (acetylacetonato) zirconium, di-tert-butoxy Bis (acetylacetonato) zirconium, monoethoxytris (acetylacetonato) zirconium, mono-n-propoxytris (acetylacetonato) zirconium, monoisopropoxytris Acetylacetonato) zirconium, mono-n-butoxy-tris (acetylacetonato) zirconium, mono-sec-butoxy-tris (acetylacetonato) zirconium, mono-tert-butoxy-tris (acetylacetonato) zirconium, tetrakis ( Acetylacetonato) zirconium, triethoxy mono (ethyl acetoacetate) zirconium, tri-n-propoxy mono (ethyl acetoacetate) zirconium, triisopropoxy mono (ethyl acetoacetate) zirconium, tri-n-butoxy mono ( Ethyl acetoacetate) zirconium, tri-sec-butoxy mono (ethyl acetoacetate) zirconium, tri-tert-butoxy mono (ethyl acetoacetate) zirconium Konium, diethoxy bis (ethyl acetoacetate) zirconium, di-n-propoxy bis (ethyl acetoacetate) zirconium, diisopropoxy bis (ethyl acetoacetate) zirconium, di-n-butoxy bis (ethyl acetoacetate) Zirconium, di-sec-butoxy bis (ethyl acetoacetate) zirconium, di-tert-butoxy bis (ethyl acetoacetate) zirconium, monoethoxy tris (ethyl acetoacetate) zirconium, mono-n-propoxy tris (ethyl) Acetoacetate) zirconium, monoisopropoxy tris (ethyl acetoacetate) zirconium, mono-n-butoxy tris (ethyl acetoacetate) zirconium, mono-sec-but Si-tris (ethylacetoacetate) zirconium, mono-tert-butoxy-tris (ethylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, mono (acetylacetonato) tris (ethylacetoacetate) zirconium, bis (acetylacetate) Zirconium chelate compounds such as nattobis (ethylacetoacetate) zirconium, tris (acetylacetonato) mono (ethylacetoacetate) zirconium; triethoxy mono (acetylacetonato) aluminum, tri-n-propoxy mono (acetylacetate) Nato) aluminum, triisopropoxy mono (acetylacetonato) aluminum, tri-n-butoxy mono (acetylacetonato) aluminium , Tri-sec-butoxy mono (acetylacetonato) aluminum, tri-tert-butoxy mono (acetylacetonato) aluminum, diethoxybis (acetylacetonato) aluminum, di-n-propoxybis (acetylacetonate) ) Aluminum, diisopropoxy bis (acetylacetonato) aluminum, di-n-butoxy bis (acetylacetonato) aluminum, di-sec-butoxy bis (acetylacetonato) aluminum, di-tert-butoxy bis (Acetylacetonato) aluminum, monoethoxy tris (acetylacetonato) aluminum, mono-n-propoxy tris (acetylacetonato) aluminum, monoisopropoxy tris (acetylacetate) Tonato) aluminum, mono-n-butoxy tris (acetylacetonato) aluminum, mono-sec-butoxy tris (acetylacetonato) aluminum, mono-tert-butoxy tris (acetylacetonato) aluminum, tetrakis (acetylacetate) Natto aluminum, triethoxy mono (ethyl acetoacetate) aluminum, tri-n-propoxy mono (ethyl acetoacetate) aluminum, triisopropoxy mono (ethyl acetoacetate) aluminum, tri-n-butoxy mono (ethyl aceto) Acetate) aluminum, tri-sec-butoxy mono (ethyl acetoacetate) aluminum, tri-tert-butoxy mono (ethyl acetoacetate) aluminum, di Toxi bis (ethyl acetoacetate) aluminum, di-n-propoxy bis (ethyl acetoacetate) aluminum, diisopropoxy bis (ethyl acetoacetate) aluminum, di-n-butoxy bis (ethyl acetoacetate) aluminum, Di-sec-butoxy bis (ethyl acetoacetate) aluminum, di-tert-butoxy bis (ethyl acetoacetate) aluminum, monoethoxy tris (ethyl acetoacetate) aluminum, mono-n-propoxy tris (ethyl acetoacetate) ) Aluminum, monoisopropoxy tris (ethyl acetoacetate) aluminum, mono-n-butoxy tris (ethyl acetoacetate) aluminum, mono-sec-butoxy tris Ethyl acetoacetate) aluminum, mono-tert-butoxy-tris (ethylacetoacetate) aluminum, tetrakis (ethylacetoacetate) aluminum, mono (acetylacetonato) tris (ethylacetoacetate) aluminum, bis (acetylacetonato) bis ( 1 type or 2 types or more of aluminum chelate compounds, such as ethyl acetoacetate) aluminum and tris (acetylacetonato) mono (ethyl acetoacetate) aluminum, etc. are mentioned.

In _{particular, (CH 3 (CH 3)} HCO) 4-t Ti (CH 3 COCH 2 COCH 3) t, (CH 3 (CH 3) HCO) 4-t Ti (CH 3 COCH 2 COOC 2 H 5) t, _{(C 4 H 9 O) 4} -t Ti (CH 3 COCH 2 COCH 3) t, (C 4 H 9 O) 4-t Ti (CH 3 COCH 2 COOC 2 H 5) t, (C 2 H 5 ( CH ₃ ) CO) _4-t Ti (CH ₃ COCH ₂ COCH ₃ ) _t , (C ₂ H ₅ (CH ₃ ) CO) _4-t Ti (CH ₃ COCH ₂ COOC ₂ H ₅ ) _t , (CH ₃ ( CH ₃ ) HCO) _4-t Zr (CH ₃ COCH ₂ COCH ₃ ) _t , (CH ₃ (CH ₃ ) HCO) _4-t Zr (CH ₃ COCH ₂ COOC ₂ H ₅ ) _t , (C ₄ H ₉ O ) _4-t Zr (CH ₃ COCH ₂ COCH ₃ ) _t , (C ₄ H ₉ O) _4-t Zr (CH ₃ COCH ₂ COOC ₂ H ₅ ) _t , (C ₂ H ₅ (CH ₃ ) CO) _4-t Zr (CH ₃ COCH _{2 COCH 3) t, (C} 2 H 5 (CH 3) CO) 4-t Zr (CH 3 COCH 2 COOC 2 H 5) t, (CH 3 (CH 3) HCO) 3-t Al (CH 3 COCH _{2 COCH 3) t, (CH} 3 (CH 3) HCO) 3-t Al (CH 3 COCH 2 COOC 2 H 5) t, (C 4 H 9 O) 3-t Al (CH 3 COCH 2 COCH 3) _{t, (C 4 H 9 O} ) 3-t Al (CH 3 COCH 2 COOC 2 H 5) t, (C 2 H 5 (CH 3) CO) 3-t Al (CH 3 COCH 2 COCH 3) t, (C ₂ H ₅ (CH ₃ ) CO) _3-t Al (CH ₃ COCH ₂ COOC ₂ H ₅ ) One or more types such as _t are preferred as the metal chelate compound used.

  The amount of the metal chelate compound used is 0.0001 to 10 parts by weight, preferably 0.001 to 5 parts by weight, based on 100 parts by weight of the total amount of silane compounds (in terms of complete hydrolysis condensate). When the use ratio of the metal chelate compound is less than 0.0001 part by weight, the coatability of the coating film may be inferior, and when it exceeds 10 parts by weight, the polymer growth cannot be controlled and gelation may occur.

  When hydrolyzing and condensing a silane compound in the presence of a metal chelate compound, it is preferable to use 0.5 to 20 mol of water per mol of the total amount of silane compounds, and it is particularly preferable to add 1 to 10 mol of water. If the amount of water to be added is less than 0.5 mol, the hydrolysis reaction does not proceed sufficiently, which may cause problems in coating properties and storage stability, and if it exceeds 20 mol, the hydrolysis and condensation reactions may occur. Polymer precipitation or gelation may occur. Moreover, it is preferable that water is added intermittently or continuously.

1.3.1-2. Acidic compound (C) As an acidic compound which can be used as a catalyst, an organic acid or an inorganic acid can be illustrated. Examples of organic acids include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid Acid, butyric acid, meritic acid, arachidonic acid, shikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfone Acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, maleic anhydride, fumaric acid, itaconic acid, succinic acid, mesaconic acid, Citraconic acid, malic acid, malonic acid, hydrolyzed glutaric acid, hydrolyzed maleic anhydride Object can include hydrolysis products of phthalic anhydride. Examples of inorganic acids include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.

  Of these, organic acids are preferred in that there is little risk of polymer precipitation or gelation during the hydrolysis-condensation reaction, and among these, compounds having a carboxyl group are more preferred, and among them, acetic acid, oxalic acid, maleic acid, formic acid. Particularly preferred are organic acids such as hydrolysates of malonic acid, phthalic acid, fumaric acid, itaconic acid, succinic acid, mesaconic acid, citraconic acid, malic acid, malonic acid, glutaric acid and maleic anhydride. These may be used alone or in combination of two or more.

  The usage-amount of an acidic compound is 0.0001-10 weight part with respect to 100 weight part (total hydrolysis condensate conversion) of the total amount of a silane compound, Preferably it is 0.001-5 weight part. When the amount of the acidic compound used is less than 0.0001 parts by weight with respect to 100 parts by weight of the total amount of the silane compound, the coating property of the coating film may be inferior. The condensation reaction may progress and cause gelation.

  When hydrolyzing and condensing a silane compound in the presence of an acidic compound, it is preferable to use 0.5 to 20 mol of water per mol of the total amount of silane compounds, and it is particularly preferable to add 1 to 10 mol of water. If the amount of water to be added is less than 0.5 mol, the hydrolysis reaction does not proceed sufficiently, which may cause problems in coating properties and storage stability, and if it exceeds 20 mol, the hydrolysis and condensation reactions may occur. Polymer precipitation or gelation may occur. Moreover, it is preferable that water is added intermittently or continuously.

1.3.1-3. Basic compounds (C) Examples of basic compounds that can be used as catalysts include methanolamine, ethanolamine, propanolamine, butanolamine, N-methylmethanolamine, N-ethylmethanolamine, N-propylmethanolamine, N -Butylmethanolamine, N-methylethanolamine, N-ethylethanolamine, N-propylethanolamine, N-butylethanolamine, N-methylpropanolamine, N-ethylpropanolamine, N-propylpropanolamine, N-butyl Propanolamine, N-methylbutanolamine, N-ethylbutanolamine, N-propylbutanolamine, N-butylbutanolamine, N, N-dimethylmethanolamine, N, N-diethylmethanol Amine, N, N-dipropylmethanolamine, N, N-dibutylmethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N-dipropylethanolamine, N, N-dibutylethanol Amine, N, N-dimethylpropanolamine, N, N-diethylpropanolamine, N, N-dipropylpropanolamine, N, N-dibutylpropanolamine, N, N-dimethylbutanolamine, N, N-diethylbutanolamine N, N-dipropylbutanolamine, N, N-dibutylbutanolamine, N-methyldimethanolamine, N-ethyldimethanolamine, N-propyldimethanolamine, N-butyldimethanolamine, N-methyldiethanolamine N-ethyldie Nolamine, N-propyldiethanolamine, N-butyldiethanolamine, N-methyldipropanolamine, N-ethyldipropanolamine, N-propyldipropanolamine, N-butyldipropanolamine, N-methyldibutanolamine, N-ethyl Dibutanolamine, N-propyldibutanolamine, N-butyldibutanolamine, N- (aminomethyl) methanolamine, N- (aminomethyl) ethanolamine, N- (aminomethyl) propanolamine, N- (aminomethyl) ) Butanolamine, N- (aminoethyl) methanolamine, N- (aminoethyl) ethanolamine, N- (aminoethyl) propanolamine, N- (aminoethyl) butanolamine, N- (aminopropyl) methano Ruamine, N- (aminopropyl) ethanolamine, N- (aminopropyl) propanolamine, N- (aminopropyl) butanolamine, N- (aminobutyl) methanolamine, N- (aminobutyl) ethanolamine, N- ( Aminobutyl) propanolamine, N- (aminobutyl) butanolamine, methoxymethylamine, methoxyethylamine, methoxypropylamine, methoxybutylamine, ethoxymethylamine, ethoxyethylamine, ethoxypropylamine, ethoxybutylamine, propoxymethylamine, propoxyethylamine, Propoxypropylamine, propoxybutylamine, butoxymethylamine, butoxyethylamine, butoxypropylamine, butoxybutylamine, methylamine , Ethylamine, propylamine, butylamine, N, N-dimethylamine, N, N-diethylamine, N, N-dipropylamine, N, N-dibutylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tetramethylammonium Hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetramethylethylenediamine, tetraethylethylenediamine, tetrapropylethylenediamine, tetrabutylethylenediamine, methylaminomethylamine, methylaminoethylamine, methylamino Propylamine, methylaminobutylamine, ethylaminomethylamine, ethylaminoethylamine Ethylaminopropylamine, ethylaminobutylamine, propylaminomethylamine, propylaminoethylamine, propylaminopropylamine, propylaminobutylamine, butylaminomethylamine, butylaminoethylamine, butylaminopropylamine, butylaminobutylamine, pyridine, pyrrole, piperazine Pyrrolidine, piperidine, picoline, morpholine, methylmorpholine, diazabicycloocrane, diazabicyclononane, diazabicycloundecene, ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, etc. Can do.

  The basic compound is particularly preferably a nitrogen-containing compound represented by the following general formula (5) (hereinafter also referred to as “compound 4”).

(X ¹ X ² X ³ X ⁴ N) _g Y (5)
In the general formula (5), X ¹ , X ² , X ³ , and X ⁴ are the same or different and are each a hydrogen atom or an alkyl group having 1 to 20 carbon atoms (preferably a methyl group, an ethyl group, a propyl group, a butyl group Hexyl group), hydroxyalkyl group (preferably hydroxyethyl group etc.), aryl group (preferably phenyl group etc.), arylalkyl group (preferably phenylmethyl group etc.), Y is a halogen atom (preferably fluorine) An atom, a chlorine atom, a bromine atom, an iodine atom, etc.), a 1 to 4 valent anionic group (preferably a hydroxy group), and g represents an integer of 1 to 4.

  Specific examples of compound 4 include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, tetra-iso-propylammonium hydroxide, tetra-n-butylammonium hydroxide, tetra-hydroxide iso-butylammonium hydroxide, tetra-tert-butylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraheptylammonium hydroxide, tetraoctylammonium hydroxide, tetranonylammonium hydroxide, tetradecylammonium hydroxide, Tetraundecyl ammonium hydroxide, tetradodecyl ammonium hydroxide, tetramethylammonium bromide, tetramethylammonium chloride, tetraethylammonium bromide, teto chloride Ethylammonium, tetra-n-propylammonium bromide, tetra-n-propylammonium chloride, tetra-n-butylammonium bromide, tetra-n-butylammonium chloride, hexadecyltrimethylammonium hydroxide, -n-hexabromide Decyltrimethylammonium hydroxide, hydroxide-n-octadecyltrimethylammonium, bromide-n-octadecyltrimethylammonium bromide, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, benzyltrimethylammonium chloride, didecyldimethylammonium chloride, distearyldimethylammonium chloride, chloride Tridecylmethylammonium, tetrabutylammonium hydrogen sulfate, tributylmethylammonium bromide, trioctyl chloride Methyl ammonium, trilauryl methyl ammonium chloride, benzyl trimethyl ammonium hydroxide, benzyl bromide triethylammonium, and the like are preferable benzyl bromide tributylammonium bromide phenyl trimethyl ammonium, choline and the like. Among these, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, tetra-n-butylammonium hydroxide, tetramethylammonium bromide, tetramethylammonium chloride, tetraethyl bromide are particularly preferable. Ammonium, tetraethylammonium chloride, tetra-n-propylammonium bromide, tetra-n-propylammonium chloride. Compound 4 may be used alone or in combination of two or more.

  The usage-amount of a basic compound is 0.00001-10 mol normally with respect to 1 mol of total amounts of the hydrolysable group in a silane compound, Preferably it is 0.00005-5 mol.

  When hydrolyzing and condensing a silane compound in the presence of a basic compound, it is preferable to use 0.5 to 20 mol of water per mol of the total amount of silane compounds, and it is particularly preferable to add 1 to 10 mol of water. If the amount of water to be added is less than 0.5 mol, the hydrolysis reaction does not proceed sufficiently, which may cause problems in coating properties and storage stability, and if it exceeds 20 mol, the hydrolysis and condensation reactions may occur. Polymer precipitation or gelation may occur. Moreover, it is preferable that water is added intermittently or continuously.

  When a basic compound is used as the (C) catalyst, an acidic compound may be used after the hydrolysis condensation reaction to adjust the pH of the composition. As the acidic compound used here, the acidic compound exemplified as the catalyst (C) can be used, and it is more preferable to use an organic acid.

1.3.2. Organic solvent Examples of the organic solvent that can be used in producing the first and second hydrolysis-condensation products include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, and sec-butanol. Alcohol solvents such as t-butanol; ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexane Polyhydric alcohol solvents such as diol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Polyhydric alcohol partial ether solvents such as ethylene glycol monopropyl ether and ethylene glycol monobutyl ether; ethyl ether, i-propyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide , Dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, and other ether solvents; acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl -N-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl -N-butyl ketone, methyl-n-hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, Examples thereof include ketone solvents such as acetonyl acetone and diacetone alcohol.

  The reaction temperature in the hydrolysis condensation for producing the first and second hydrolysis condensates is 0 to 100 ° C., preferably 20 to 80 ° C., and the reaction time is 30 to 1000 minutes, preferably 30 to 180 minutes. .

1.3.3. Production of Film-Forming Composition The film-forming composition according to this embodiment can be obtained by separately producing the first hydrolysis condensate and the second hydrolysis condensate and mixing them. . For example, by mixing the first composition containing the first hydrolysis condensate and the organic solvent and the second composition containing the second hydrolysis condensate and the organic solvent, according to the present embodiment A film-forming composition can be obtained.

1.4. Organic Solvents Organic solvents that can be used in the composition for forming an insulating film according to this embodiment include alcohol solvents, ketone solvents, amide solvents, ether solvents, ester solvents, aliphatic hydrocarbon solvents, aromatics. And at least one selected from the group of group solvents and halogen-containing solvents.

Examples of alcohol solvents include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec -Pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, full Lil alcohol, phenol, cyclohexanol, methyl cyclohexanol, 3,3,5-trimethyl cyclohexanol, benzyl alcohol, mono-alcohol solvents such as diacetone alcohol;
Ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2 Polyhydric alcohol solvents such as ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol;
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol And the like; monomethyl ether, dipropylene glycol monoethyl ether, polyhydric alcohol partial ether solvents such as dipropylene glycol monopropyl ether. These alcohol solvents may be used alone or in combination of two or more.

  Examples of ketone solvents include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, and methyl-n-hexyl. Ketone, di-i-butyl ketone, trimethylnonanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, Mention may be made of ketone solvents such as fenchon. These ketone solvents may be used alone or in combination of two or more.

  Examples of amide solvents include N, N-dimethylimidazolidinone, N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N- Examples thereof include nitrogen-containing solvents such as methylpropionamide and N-methylpyrrolidone. These amide solvents may be used alone or in combination of two or more.

  As ether solvents, ethyl ether, i-propyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane, ethylene Glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether , Ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol Dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di-n-butyl ether, propylene glycol Monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, diphenyl ether Le, can be mentioned ether solvents such as anisole. These ether solvents may be used alone or in combination of two or more.

  Examples of ester solvents include diethyl carbonate, propylene carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-acetate. Butyl, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methyl pentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methyl cyclohexyl acetate, n-nonyl acetate, methyl acetoacetate , Ethyl acetoacetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n acetate -Butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate, methoxy acetate Triglycol, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate And ester solvents such as dimethyl phthalate and diethyl phthalate. These ester solvents may be used alone or in combination of two or more.

  Examples of the aliphatic hydrocarbon solvent include n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i-octane, Examples thereof include aliphatic hydrocarbon solvents such as cyclohexane and methylcyclohexane. These aliphatic hydrocarbon solvents may be used alone or in combination of two or more.

  Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propyl benzene, i-propyl benzene, diethyl benzene, i-butyl benzene, triethyl benzene, di-i-propyl benzene, Aromatic hydrocarbon solvents such as n-amylnaphthalene and trimethylbenzene can be mentioned. These aromatic hydrocarbon solvents may be used alone or in combination of two or more. Examples of the halogen-containing solvent include halogen-containing solvents such as dichloromethane, chloroform, chlorofluorocarbon, chlorobenzene, and dichlorobenzene.

  In the composition for forming an insulating film according to the present embodiment, it is desirable to use an organic solvent having a boiling point of less than 150 ° C., and examples of the solvent species include alcohol solvents, ether solvents, ketone solvents, and ester solvents. It is particularly desirable to further use one or more of them at the same time.

  These organic solvents may be the same as those used for the synthesis of the hydrolysis condensate, or after the synthesis of the hydrolysis condensate is completed, the organic solvent used for the synthesis is replaced with a desired organic solvent. You can also

  The total solid concentration of the film-forming composition according to one embodiment of the present invention is preferably 0.1 to 20% by mass, and is appropriately adjusted according to the purpose of use. When the total solid content concentration of the film-forming composition according to one embodiment of the present invention is 0.1 to 20% by mass, the film thickness of the coating film is in an appropriate range and has better storage stability. It will be a thing. In addition, adjustment of this total solid content concentration is performed by concentration and dilution with an organic solvent, if necessary.

1.5. Other Additives Components such as organic polymers and surfactants may be further added to the film forming composition according to this embodiment.

1.5.1. Organic Polymer The film forming composition according to the present embodiment can further contain an organic polymer as a film hollow hole forming agent.

  Organic polymers include, for example, polymers having a sugar chain structure, vinylamide polymers, (meth) acrylic polymers, aromatic vinyl compound polymers, dendrimers, polyimides, polyamic acids, polyarylenes, polyamides, poly Examples thereof include quinoxaline, polyoxadiazole, a fluorine-based polymer, and a polymer having a polyalkylene oxide structure.

  Examples of the polymer having a polyalkylene oxide structure include a polymethylene oxide structure, a polyethylene oxide structure, a polypropylene oxide structure, a polytetramethylene oxide structure, and a polybutylene oxide structure.

  Specifically, polyoxymethylene alkyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene sterol ether, polyoxyethylene lanolin derivative, ethylene oxide derivative of alkylphenol formalin condensate, polyoxyethylene polyoxy Ether type compounds such as propylene block copolymer, polyoxyethylene polyoxypropylene alkyl ether, ethers such as polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene fatty acid alkanolamide sulfate Ester type compound, polyethylene glycol fatty acid ester, ethylene glycol fat Esters, fatty acid monoglycerides, polyglycerol fatty acid esters, sorbitan fatty esters, propylene glycol fatty acid esters, and the like ether ester type compounds such as sucrose fatty acid esters.

  Examples of the polyoxyethylene polyoxypropylene block copolymer include compounds having the following block structure.

− (X ′) ₁ − (Y ′) _m −
-(X ') _1- (Y') _m- (X ') _n-
(Wherein X ′ represents a group represented by —CH ₂ CH ₂ O—, Y ′ represents a group represented by —CH ₂ CH (CH ₃ ) O—, l is 1 to 90, and m is 10 to 99, n represents a number from 0 to 90)
Among these, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, Ether-type compounds such as polyoxyethylene sorbitol fatty acid esters can be mentioned as more preferred examples. The aforementioned organic polymers may be used alone or in combination of two or more.

1.5.2. Surfactant Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and further, fluorine surfactants, silicone surfactants, and the like. Activators, polyalkylene oxide surfactants, poly (meth) acrylate surfactants and the like can be mentioned, and fluorine surfactants and silicone surfactants can be preferably exemplified.

  The amount of the surfactant used is usually 0.00001 to 1 part by weight with respect to 100 parts by weight of the obtained hydrolysis condensate. These may be used alone or in combination of two or more.

2. Method for Forming Silica-Based Film A method for forming a silica-based film (insulating film) according to an embodiment of the present invention includes a step of applying the film-forming composition to a substrate to form a coating film, and curing to the coating film. And a process of applying a treatment.

Examples of the substrate on which the film-forming composition is applied include Si-containing layers such as Si, SiO ₂ , SiN, SiC, and SiCN. As a method for applying the film-forming composition to the substrate, a coating means such as spin coating, dipping method, roll coating method, spray method or the like is used. After the film forming composition is applied to the substrate, the solvent is removed to form a coating film. In this case, as a dry film thickness, a coating film having a thickness of 0.05 to 2.5 μm can be formed by one coating and a thickness of 0.1 to 5.0 μm can be formed by two coatings. Then, a silica-type film | membrane can be formed by performing a hardening process with respect to the obtained coating film.

  Examples of the curing treatment include heating, irradiation with high energy rays such as electron beams and ultraviolet rays, plasma treatment, and combinations thereof. Heat treatment or a combination of heat treatment and irradiation with high energy rays (ultraviolet rays) is preferable. .

  In the case of curing by heating, the coating film is heated to 80 to 450 ° C. (preferably 300 ° C. to 450 ° C.) under an inert atmosphere or reduced pressure. As a heating method at this time, a hot plate, an oven, a furnace, or the like can be used, and a heating atmosphere can be performed under an inert atmosphere or under reduced pressure.

  Moreover, in order to control the curing rate of the coating film, it can be heated stepwise or an atmosphere such as nitrogen, air, oxygen, or reduced pressure can be selected as necessary. Through such a process, a silica-based film can be manufactured.

3. Silica-based film A silica-based film according to an embodiment of the present invention has a low dielectric constant and excellent surface flatness. Therefore, an interlayer for semiconductor elements such as LSI, system LSI, DRAM, SDRAM, RDRAM, and D-RDRAM is used. It is particularly excellent as an insulating film, and it is an etching stopper film, a protective film such as a surface coating film of a semiconductor element, an intermediate layer of a semiconductor manufacturing process using a multilayer resist, an interlayer insulating film of a multilayer wiring board, and a liquid crystal display element It can be suitably used for a protective film or an insulating film. The silica-based film according to this embodiment is useful for a semiconductor device including a copper damascene process.

The silica-based film according to the present embodiment has a relative dielectric constant of preferably 1.8 to 4.0, more preferably 2.0 to 3.5, and an elastic modulus of preferably 2 to 50 GPa. more preferably 3～50GPa, the film density is preferably 0.7~1.8g / cm ^3, more preferably 0.8 to 1.5 g / cm ^3. From these facts, it can be said that the organic silica film according to this embodiment is extremely excellent in insulating film characteristics such as mechanical characteristics, low hygroscopicity, and low relative dielectric constant.

4). EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited to the following examples. In the examples and comparative examples, “parts” and “%” indicate parts by weight and mass%, respectively, unless otherwise specified.

4.1. Evaluation method Various evaluations were performed as follows.

4.1.1. A dielectric constant measurement sample was prepared by forming an aluminum electrode pattern on an organic silica film formed on an N-type silicon wafer of 8 inches having a resistivity of 0.1 Ω · cm or less by vapor deposition. . The relative dielectric constant of the organic silica film was measured at 200 ° C. by the CV method using an HP16451B electrode and an HP4284A precision LCR meter manufactured by Agilent at a frequency of 100 kHz.

4.1.2. Elastic modulus A Berkovich indenter was attached to an ultra-small hardness meter (Nanoindentator XP) manufactured by MTS, and the elastic modulus of the organic silica film formed by the following method was measured by a continuous stiffness measurement method.

4.1.3. Chemical Solution Resistance An 8-inch wafer on which a polymer film was formed was immersed in a 0.2% dilute hydrofluoric acid aqueous solution at room temperature for 1 minute, and the change in film thickness before and after immersion of the polymer film was observed. If the remaining film rate defined below is 99% or more, it is judged that the chemical solution resistance is good (indicated by “A” in Table 1), and if the remaining film rate is less than 99%, the chemical solution resistance is poor. (Indicated by “B” in Table 1).

Remaining film ratio (%) = (film thickness after immersion) / (film thickness before immersion) × 100
4.1.4. Weight average molecular weight; Mw
Weight average molecular weight of hydrolysis condensate; Mw was measured by size exclusion chromatography (SEC) method under the following conditions.

Sample: Concentration 10 mmol / L LiBr—H ₃ PO ₄ 2-methoxyethanol solution was used as a solvent, and hydrolysis condensate 0.1 g was dissolved in 100 cc 10 mmol / L LiBr—H ₃ PO ₄ 2-methoxyethanol solution. Prepared.

  Standard sample: Polyethylene oxide manufactured by WAKO was used.

Equipment: High-speed GPC equipment (model HLC-8120GPC) manufactured by Tosoh Corporation
Column: Three TSK-GEL SUPER AWM-H (length: 15 cm) manufactured by Tosoh Corporation were used in series.

Measurement temperature: 40 ° C
Flow rate: 0.6 ml / min.
Detector: Detected by RI of a high-speed GPC device (model HLC-8120GPC) manufactured by Tosoh Corporation.

4.2. Synthesis examples, examples, and comparative examples 4.2.1. Synthesis example 1
In a quartz-separable flask substituted with nitrogen, 60.9 g of methyltrimethoxysilane, 177.3 g of tetramethoxysilane, and 599.1 g of propylene glycol monoethyl ether were added and heated to 60 ° C. in a water bath. The acid aqueous solution 2.3g and the ultrapure water 160.4g were added, and it was made to stir at 60 degreeC for 5 hours. This solution was concentrated under reduced pressure to a total solution amount of 500 g to a solid content of 20%, and then diluted with propylene glycol monoethyl ether to a solid content of 10% to obtain a composition solution (A). . The molecular weight of the polysiloxane obtained from this synthesis example was 2,300.

4.2.2. Synthesis example 2
In a nitrogen-substituted quartz separable flask, 101.5 g of methyltrimethoxysilane, 134.1 g of bis (triethoxysilyl) ethane, and 642.3 g of propylene glycol monoethyl ether were added and heated to 60 ° C. in a water bath. Thereafter, 2.2 g of 20% maleic acid aqueous solution and 120.0 g of ultrapure water were added and stirred at 60 ° C. for 5 hours. The solution was concentrated under reduced pressure to a total solution amount of 500 g to a solid content of 20%, and then diluted with propylene glycol monoethyl ether to a solid content of 10% to obtain a composition solution (B). . The molecular weight of the polysiloxane obtained from this synthesis example was 3,700.

4.2.3. Synthesis example 3
In a nitrogen-substituted quartz separable flask, 253.3 g of tetramethoxysilane and 506.7 g of propylene glycol monoethyl ether were added, heated to 60 ° C. in a water bath, and then 0.010 g of tetrakis (acetylacetonate) titanium, 239.9 g of ultrapure water was added and stirred at 60 ° C. for 2 hours. This solution was concentrated under reduced pressure to a total solution amount of 500 g to a solid content of 20%, and then diluted with propylene glycol monoethyl ether to a solid content of 10% to obtain a composition solution (C). . The molecular weight of the polysiloxane obtained from this synthesis example was 4,100.

4.2.4. Synthesis example 4
101.5 g of methyltrimethoxysilane, 76.0 g of tetramethoxysilane, and 643.0 g of propylene glycol monoethyl ether were added to a quartz-separable flask substituted with nitrogen, heated to 60 ° C. in a water bath, The acid aqueous solution 1.9g and the ultrapure water 137.0g were added, and it was made to stir at 60 degreeC for 5 hours. This solution was concentrated under reduced pressure to a total solution amount of 500 g to a solid content of 20%, and then diluted with propylene glycol monoethyl ether to a solid content of 10% to obtain a composition solution (D). . The molecular weight of the polysiloxane obtained from this synthesis example was 1,900.

4.2.5. Synthesis example 5
In a nitrogen-substituted quartz separable flask, 172.5 g of methyltrimethoxysilane, 38.0 g of tetramethoxysilane, and 616.6 g of propylene glycol monomethyl ether were added and heated to 60 ° C. in a water bath, followed by tetrakis (acetylacetate). Natto) 0.010 g of titanium and 172.9 g of ultrapure water were added and stirred at 60 ° C. for 2 hours. This solution was concentrated under reduced pressure to a total solution amount of 500 g to a solid content of 20%, and then diluted with propylene glycol monomethyl ether to a solid content of 10% to obtain a composition solution (E). The molecular weight of the polysiloxane obtained from this synthesis example was 1,500.

4.2.6. Examples 1-5 and Comparative Examples 1-14
The composition solution obtained in each synthesis example was mixed at a weight ratio shown in Table 1 to prepare a coating composition. As for the example in which “PE-61” is used as an additive, 60 parts of polyoxyethylene polyoxypropylene block copolymer “PE-61” manufactured by Sanyo Chemical Industries, Ltd. is added to the composition solution in terms of solid content of polysiloxane. did. Next, this was coated on an 8-inch silicon wafer by spin coating, and heated in the atmosphere at 80 ° C. for 5 minutes and then at 200 ° C. for 5 minutes under nitrogen. Furthermore, the crosslinking process was implemented by the method shown by each example, and the colorless and transparent film | membrane was formed. The evaluation results of the solution and the film are shown in Table 1. The crosslinking treatment method is as follows.

(Heat treatment)
Heated under vacuum at 425 ° C. for 1 hour.

(UV)
Ultraviolet rays were irradiated while heating the coating film at 400 ° C. on a hot plate in a chamber having an oxygen partial pressure of 0.01 kPa. As the ultraviolet light source, white ultraviolet light having a wavelength of 250 nm or less was used. Since this ultraviolet light is white ultraviolet light, the illuminance cannot be measured by an effective method.

4.3. Discussion (1) The films obtained in Examples 1 and 2 were formed using a composition obtained by mixing Composition A and Composition D. Although the films obtained in Examples 1 and 2 are almost the same in relative dielectric constant and elastic modulus as compared with the film formed by using only Composition A (Comparative Example 1), It can be seen that the chemical resistance is improved. Moreover, in Comparative Example 2, it is a film formed using only the composition D, and although the chemical resistance is excellent, the mechanical properties are inferior. (2) Examples 3 and 4 and Comparative Examples 3 and 4 Are obtained by changing the crosslinking treatment of Examples 1 and 2 and Comparative Examples 1 and 2 from thermal firing to ultraviolet treatment, and in this case, the same tendency as in the above (1) appears.

  (3) Example 5-7 was formed using a composition obtained by mixing composition B and composition E. According to Example 5-7, it can be seen that the film formed using the mixture of Compositions B and E has a high elastic modulus and excellent chemical resistance, and exhibits the effects of the present invention. It turns out that it is excellent in chemical | medical solution tolerance compared with the film | membrane (comparative example 5) formed using the composition B independently. Moreover, it turns out that an elasticity modulus is high compared with the film | membrane (comparative example 6) formed using the composition E independently.

  (4) The compositions used in Examples 8-10 and Comparative Examples 7 and 8 contain an organic polymer for the purpose of reducing the relative dielectric constant. According to Examples 8-10, it can be seen that the film formed using the mixture of Compositions B and E has a high elastic modulus and excellent chemical resistance, and exhibits the effects of the present invention.

  (5) In Examples 11 and 12 and Comparative Example 9, a film was formed using a mixture of Composition C synthesized using only a tetrafunctional silane compound (Compound 1) and Composition D. Between Examples 11 and 12 and Comparative Example 9, the same relationship as that of Examples 1 and 2 and Comparative Example 1 in (1) described above is established.

Claims (7)

50-100 mol% of at least one silane compound selected from the group of compounds represented by the following general formula (1) and the following general formula (2), and 0-50 mol of other silane compounds A first hydrolytic condensate obtained by hydrolytic condensation of
A second hydrolysis-condensation product obtained by hydrolytic condensation of more than 50 mol% of at least one silane compound represented by the following general formula (3) and less than 50 mol% of another silane compound;
An organic solvent,
Including
The composition for insulating film formation whose weight average molecular weights of said 1st hydrolysis-condensation product and said 2nd hydrolysis-condensation product are 700 or more and 20,000 or less.
Si (OR ¹ ) ₄ (1)
(In the formula, R ¹ represents a monovalent organic group.)
_{^{R 2 a (R 3 O)}} 3-a Si- (R 6) c -Si (OR 4) 3-b R 5 b ··· (2)
(Wherein R ^{2 to} R ⁵ independently represent a monovalent organic group, a and b each independently represents a number of 0 to 1, and R ⁶ represents an oxygen atom, a phenylene group or — (CH ₂ ) represents a group represented by _m- (where m is an integer of 1 to 6), and c represents 0 or 1.)
R ⁷ _d Si (OR ⁸ ) _4-d (3)
(In formula, R < ⁷ > -R < ⁸ > represents a monovalent organic group independently, d shows the number of 1-2.) In claim 1,
The said other silane compound for obtaining a 1st hydrolysis-condensation product is a compound for insulating film formation which is a compound represented by the said General formula (3). In claim 1 or 2,
The said other silane compound for obtaining a 2nd hydrolysis-condensation product is a compound for insulating film formation which is a compound represented by the said General formula (1). In any one of Claims 1 thru | or 3,
The composition for insulating film formation whose ratio of this 1st hydrolysis-condensation product with respect to the total amount of said 1st hydrolysis-condensation product and said 2nd hydrolysis-condensation product is 5-95 mass%. In any of claims 1 to 4,
An insulating film forming composition further comprising an organic polymer as a film hollow hole forming agent.   The formation of a silica-based film, comprising: a step of applying the insulating film-forming composition according to claim 1 to a substrate to form a coating film; and a step of curing the coating film. Method.   A silica-based film obtained by the method for forming a silica-based film according to claim 6.