JP2008198852A - Insulating film formation composition, as well as, silica system film and its forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an insulating film formation composition, silica system film, and its formation method, which is used suitably in semiconductor devices expected to have high integration and multilayering or the like, excellent in storage stability, low in specific inductive capacity, and usable for forming an insulating film excellent in mechanical strength. <P>SOLUTION: The insulating film formation composition contains hydrolytic condensation compound obtained by the hydrolytic condensation of a component (A); in a formula (1) compound expressed with a general formula Si(OR<SP>1</SP>)<SB>4</SB>, and 50-100 mol% of at least a kind of silane compound selected from the group of compounds expressed with a general formula (2): R<SP>2</SP><SB>a</SB>(R<SP>3</SP>O)<SB>3-a</SB>Si-(R<SP>6</SP>)<SB>c</SB>-Si(OR<SP>4</SP>)<SB>3-b</SB>R<SP>5</SP><SB>b</SB>, and of a constituent (B): 0-50 mol% of other hydrolytic silane compounds, and organic solvent, wherein the pH is in the range of 3.0-5.0 and the amount of water contents is 2 mass% or below. In the formula (1), R<SP>1</SP>shows monovalent organic group. In the formula (2), R<SP>2</SP>-R<SP>5</SP>are identical or different, show respectively monovalent organic group, a and b are identical or different, show the number of 0-1, R<SP>6</SP>expresses oxygen atom, phenylene group or group expressed by -(CH<SB>2</SB>)<SB>m</SB>- (here, m expresses integral number of 1-6), and c shows 0 or 1. <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 has been frequently 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.

Usually, an organic silica sol composition for a low relative dielectric constant insulating film used in a semiconductor device is subjected to thermal curing in consideration of the yield in a process in which mechanical stress such as CMP (Chemical Mechanical Polishing) or packaging occurs. 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 is 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, since it is difficult to completely react the crosslinking site (silanol) of these silane compounds, the hydrolysis condensation reaction proceeds gradually in the composition for forming an insulating film, and the film thickness changes at the time of coating, Storage stability may be low due to generation of foreign matter or increase in viscosity.
US Pat. No. 6,495,264

  The object of the present invention can be suitably used in a semiconductor device or the like for which high integration and multilayering are desired, and has excellent storage stability, low relative permittivity, and excellent mechanical strength. An object of the present invention is to provide a composition for forming an insulating film that can be used for forming a film.

  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:
(A) component; 50-100 mol% of at least 1 sort (s) of silane compounds chosen from the group of the compound represented by the compound represented by the following general formula (1), and the following general formula (2), (B) A component; a hydrolytic condensate obtained by hydrolytic condensation of 0 to 50 mol% of another hydrolyzable silane compound, and an organic solvent,
The pH is in the range of 3.0 to 5.0, and the water content is 2% by mass 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 are the same or different and each represents a monovalent organic group, a and b are the same or different and represent 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.)

  In the present invention, “hydrolyzable” means having a group that can be hydrolyzed during the hydrolytic condensation of the silane compound.

In the composition for forming an insulating film, the component (B) can be a compound represented by the following general formula (3).
R ⁷ _d Si (OR ⁸ ) _4-d (3)
(Wherein R ⁷ represents a hydrogen atom, a fluorine atom, or a monovalent organic group, R ⁸ represents a monovalent organic group, and d represents an integer of 1 to 3)

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

A 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 subjecting the coating film to a curing treatment.

  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 hydrolyzed condensate obtained by hydrolytic condensation of the component (A) and the component (B), and an organic solvent, have a pH of 3.0. In the range of ˜5.0 and the moisture content is 2% by mass or less, it is possible to form an insulating film having excellent storage stability, excellent mechanical strength, and low relative dielectric constant. .

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

  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 Forming Insulating Film and Production Thereof The composition for forming an insulating film according to one embodiment of the present invention comprises a component (A); a compound represented by the following general formula (1) (hereinafter also referred to as “compound 1”) And at least one silane compound selected from the group of compounds represented by the following general formula (2) (hereinafter also referred to as “compound 2”), component (B); A hydrolytic condensate obtained by hydrolytic condensation of 0 to 50 mol% of the hydrolyzable silane compound, and an organic solvent, and the pH is in the range of 3.0 to 5.0, and The water content is 2% by mass 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 are the same or different and each represents a monovalent organic group, a and b are the same or different and represent 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.)

  When the pH of the composition for forming an insulating film according to this embodiment is less than 3 or more than 5, the condensation of the silica sol tends to proceed, and the viscosity tends to increase or gelate. For this reason, it is preferable that the pH of the composition for insulating film formation concerning this embodiment is 3-5, and it is more preferable that it is 3-4.5.

  The water content of the composition for forming an insulating film according to the present embodiment is, for example, 2% by mass or less by a method of reducing the water content by concentration after hydrolysis condensation or a method of reducing the water content used during hydrolysis condensation. Can be adjusted.

  In addition, when the water content of the composition for forming an insulating film according to the present embodiment exceeds 2% by mass, the condensation of the silica sol tends to proceed, and the viscosity is likely to increase or gelate. The water content of the composition for forming an insulating film according to this embodiment is more preferably 1.5% by mass or less.

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

1.1. Hydrolysis condensate 1.1.1. (A) component (A) component used in order to obtain a hydrolysis-condensation product can condense (A) component, and can form a Si-O-Si bond. Moreover, when using (B) component, it can further condense with (B) component and can form a Si-O-Si bond. In the present invention, as a raw material used for obtaining the hydrolysis condensate, the component (A) is contained in an amount of 50 to 100 mol% (raw material ratio) of the total silane compound, preferably 65 to 100 mol%, Preferably it contains 85 mol%-100 mol%.

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. These 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. (B) Component Examples of the other hydrolyzable silane compound as the component (B) include a compound represented by the general formula (3) described later.

More specifically, the other silane compound as the component (B) is preferably a compound represented by the following general formula (3) (hereinafter also referred to as “compound 3”).
R ⁷ _d Si (OR ⁸ ) _4-d (3)
(Wherein R ⁷ represents a hydrogen atom, a fluorine atom, or a monovalent organic group, R ⁸ represents a monovalent organic group, and d represents an integer of 1 to 3)

In the general formula (3), examples of the monovalent organic groups 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.

  Particularly preferred compounds as 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.

1.1.3. (C) Catalyst (C) A catalyst can be used when hydrolyzing and condensing a silane compound. (C) The catalyst is preferably at least one compound selected from a basic compound, an acidic compound, and a metal chelate compound.

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 the silane compound in the presence of the metal chelate compound, in order to adjust the water content of the resulting composition to 2% by mass or less, 0.5 to 20 moles per mole of the total amount of silane compounds Water is preferably used, and 1 to 10 mol of water is particularly preferably added. 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, when not removing water | moisture content by concentration etc., in order to adjust the moisture content of the composition obtained to 2 mass% or less, it is 0.5-1 .1 with respect to 1 mol of total amounts of a hydrolysable substituent. 5, preferably 0.5 to 1.0 mol of water is used. In addition, it is preferable that water is added intermittently or continuously.

1.1-3-2. 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 the pH of the composition is easily adjusted to the range of 3.0 to 5.0. More preferred are compounds having acetic acid, oxalic acid, maleic acid, formic acid, malonic acid, phthalic acid, fumaric acid, itaconic acid, succinic acid, mesaconic acid, citraconic acid, malic acid, malonic acid, glutaric acid, Organic acids such as hydrolysates of maleic anhydride are particularly preferred. 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, in order to adjust the water content of the resulting composition to 2% by mass or less, 0.5 to 20 mol of water per 1 mol of the total amount of the silane compound It is preferable to use 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, when not removing water | moisture content by concentration etc., in order to adjust the moisture content of the composition obtained to 2 mass% or less, it is 0.5-1 .1 with respect to 1 mol of total amounts of a hydrolysable substituent. 5, preferably 0.5 to 1.0 mol of water is used. In addition, it is preferable that water is added intermittently or continuously.

1.1-3. 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 a basic compound is used as the catalyst (C), it is preferable to adjust the pH of the composition to a range of 3.0 to 5.0 using an acidic compound after the hydrolysis condensation reaction. 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.

1.1.4. Organic solvent Examples of the organic solvent that can be used in producing the hydrolysis-condensation product include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, and the like. Alcohol solvents; ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4- Polyhydric alcohol solvents such as heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol Polyhydric alcohol partial ether solvents such as rumonopropyl 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 Ether solvents such as 4-methyldioxolane, dioxane, dimethyldioxane, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether; 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, acetonylacetone And ketone solvents such as diacetone alcohol.

  The reaction temperature in the hydrolytic condensation of the silane compound is 0 to 100 ° C., preferably 20 to 80 ° C., and the reaction time is 30 to 1000 minutes, preferably 30 to 180 minutes.

1.2. Organic Solvent The organic solvent that can be used in the film forming composition according to this embodiment includes alcohol solvents, ketone solvents, amide solvents, ether solvents, ester solvents, aliphatic hydrocarbon solvents, aromatic solvents. Examples thereof include at least one selected from the group of system 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 as the solvent species, alcohol solvents, ketone solvents, and ester solvents are particularly desirable. It is desirable to 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.

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

1.3.1. 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 aryl ether (additional), polyoxyethylene polyethylene phenyl ether, polyoxyethylene sterol ether, polyoxyethylene lanolin derivative, alkylphenol formalin condensate Ethylene oxide derivatives, polyoxyethylene polyoxypropylene block copolymers, ether type compounds such as polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene Ether ester type compounds such as oxyethylene fatty acid alkanolamide sulfate, polyethylene glycol Call fatty acid esters, ethylene glycol fatty acid esters, fatty acid monoglycerides, polyglycerol fatty acid esters, sorbitan fatty acid 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 polyoxypropylene block copolymer, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, More preferred examples include ether type compounds. The aforementioned organic polymers may be used alone or in combination of two or more.

1.3.2. 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, and heat treatment or irradiation with high energy 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 1.5 to 4.0, more preferably 1.8 to 3.5, and an elastic modulus of preferably 1 to 100 GPa, more preferably 2～50GPa, the film density is preferably 0.7~1.5g / cm ^3, more preferably 0.8 to 1.4 g / cm ^3. From these, it can be said that the organic silica film according to the present embodiment is extremely excellent in insulating film characteristics such as mechanical characteristics, chemical resistance, 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. Dielectric constant measurement, Δk
A film-forming composition was applied onto an 8-inch N-type silicon wafer having a resistivity of 0.1 Ω · cm or less by using a spin coating method, and then on a hot plate at 90 ° C. for 3 minutes, and then in a nitrogen atmosphere The film was dried at 200 ° C. for 3 minutes and further baked for 1 hour in a vertical furnace at 420 ° C. under reduced pressure of 50 mTorr (vacuum atmosphere) to obtain a film.

  An aluminum electrode pattern was formed on the obtained film by a vapor deposition method, and a sample for measuring relative permittivity was prepared. With respect to the sample, the relative dielectric constant of the film at room temperature (24 ° C.) was measured at a frequency of 100 kHz by the CV method using an HP 16451B electrode and HP 4284A precision LCR meter manufactured by Agilent.

4.1.2. Evaluation of Elastic Modulus (Young's Modulus) of Film The elastic modulus of the film was measured by a continuous stiffness measurement method. The elastic modulus was measured for a polymer film (silica film) formed by the following method. That is, the composition obtained in each example and comparative example was applied on a silicon wafer by spin coating, and then the substrate was dried on a hot plate at 90 ° C. for 3 minutes and in a nitrogen atmosphere at 200 ° C. for 3 minutes. Further, the substrate was baked with a hot plate for 60 minutes in a nitrogen atmosphere at 400 ° C. to obtain a polymer film having a thickness of 500 μm, and this polymer film was used for evaluation of the elastic modulus.

4.1.3. pH
The pH of the hydrolysis condensate was measured at 25 ° C. using a pH meter (model name “MP225”) manufactured by METTLER TOLEDO and a pH electrode (model name “InLab 413”) manufactured by METTLER TOLEDO.

4.1.4. Water content The water content of the hydrolyzed condensate was measured by using the Karl Fischer coulometric method trace moisture measuring device (model name “AQ-7”) manufactured by Hiranuma Sangyo Co., Ltd. ) And the generation solution (trade name “AQUALITE RS” (manufactured by Hayashi Junyaku)).

4.1.5. Weight average molecular weight Mw
The weight average molecular weight (Mw) of the hydrolysis condensate was measured by a size exclusion chromatography (SEC) method under the following conditions.
Sample: A 2-methoxyethanol solution of LiBr—H ₃ PO _{4 at} a concentration of 10 mmol / L was used as a solvent, and 0.1 g of a hydrolysis condensate was added to 100 cc of 10 mmol / L LiBr—H ₃ PO _{4 in} a 2-methoxyethanol solution. And dissolved.
Standard sample: Polyethylene oxide manufactured by WAKO was used.
Apparatus: A high-speed GPC apparatus (model HLC-8120GPC) manufactured by Tosoh Corporation was used.
Column: Tosoh Co., Ltd. product, TSK-GEL SUPER AWM-H (15 cm in length) was installed in series and used.
Measurement temperature: 40 ° C
Flow rate: 0.6 ml / min.
Detector: Detected by RI of a built-in high-speed GPC device (model HLC-8120GPC) manufactured by Tosoh Corporation.

4.1.6. Storage stability 80 ml of the film-forming composition obtained in each Example and Comparative Example was placed in a glass screw cap bottle having a capacity of 100 ml, sealed, and left in an autoclave at 40 ° C. for 1 month. Samples before and after standing were applied under spin coating conditions of 2500 rpm for 30 seconds, and the film thickness when fired by the method described in the Examples and Comparative Examples was measured by an optical film thickness meter (Spectra Laser200, manufactured by Rudolph Technologies). And the rate of change in film thickness = {[(film thickness of the sample after standing−film thickness of the sample before leaving) / film thickness of the sample before standing] × 100} was calculated according to the following criteria: evaluated.
A: Change rate of film thickness <5%
B: Film thickness change rate <10%
C: Film thickness change rate ≧ 10%

4.2. Production of film-forming composition and film formation 4.2.1. Example 1
In a quartz separable flask substituted with nitrogen, 60.9 g of methyltrimethoxysilane (component (B)), 177.3 g of tetramethoxysilane (component (A)), and 599.1 g of propylene glycol monoethyl ether were added. After heating this to 60 ° C. in a water bath, 2.3 g of 20% oxalic acid aqueous solution and 160.4 g of ultrapure water were added and stirred at 60 ° C. for 5 hours. The liquid was concentrated under reduced pressure to a total solution amount of 500 g to a solid content of 20%, diluted with propylene glycol monoethyl ether to a solid content of 10%, and a composition containing a hydrolysis condensate was obtained. Obtained.

  The obtained composition was applied onto an 8-inch silicon wafer by spin coating, heated in the atmosphere at 80 ° C. for 5 minutes, then under nitrogen at 200 ° C. for 5 minutes, and further heated in vacuum at 425 ° C. for 1 hour, A colorless and transparent film was formed. The evaluation results of the composition and film are shown in Table 1.

4.2.2. Example 2
In a quartz separable flask substituted with nitrogen, 60.9 g of methyltrimethoxysilane (component (B)), 177.3 g of tetramethoxysilane (component (A)), and 599.1 g of propylene glycol monoethyl ether were added. After heating to 60 ° C. in a water bath, 2.3 g of 20% oxalic acid aqueous solution and 63.1 g of ultrapure water were added and stirred at 60 ° C. for 5 hours to obtain a composition containing a hydrolysis condensate.

  The obtained composition was applied onto an 8-inch silicon wafer by spin coating, heated in the atmosphere at 80 ° C. for 5 minutes, then under nitrogen at 200 ° C. for 5 minutes, and further heated in vacuum at 425 ° C. for 1 hour, A colorless and transparent film was formed. The evaluation results of the composition and film are shown in Table 1.

4.2.3. Comparative Example 1
In a quartz separable flask substituted with nitrogen, 60.9 g of methyltrimethoxysilane (component (B)), 177.3 g of tetramethoxysilane (component (A)), and 599.1 g of propylene glycol monoethyl ether were added. After heating this to 60 ° C. in a water bath, 2.3 g of 20% oxalic acid aqueous solution and 160.4 g of ultrapure water were added and stirred at 60 ° C. for 5 hours to obtain a composition containing a hydrolysis condensate.

  The obtained composition was applied onto an 8-inch silicon wafer by spin coating, heated in air at 80 ° C. for 5 minutes, then in a nitrogen atmosphere at 200 ° C. for 5 minutes, and further heated in vacuum at 425 ° C. for 1 hour. A colorless and transparent film was formed. The evaluation results of the composition and film are shown in Table 1.

4.2.4. Comparative Example 2
In a quartz separable flask substituted with nitrogen, 60.9 g of methyltrimethoxysilane (component (B)), 177.3 g of tetramethoxysilane (component (A)), and 599.1 g of propylene glycol monoethyl ether were added. At room temperature, 2.3 g of 20% nitric acid aqueous solution and 160.4 g of ultrapure water were added and stirred at 25 ° C. for 5 hours. The liquid was concentrated under reduced pressure to a total solution amount of 500 g to a solid content of 20%, diluted with propylene glycol monoethyl ether to a solid content of 10%, and a composition containing a hydrolysis condensate was obtained. Obtained.

  The obtained composition was applied onto an 8-inch silicon wafer by spin coating, heated in the atmosphere at 80 ° C. for 5 minutes, then under nitrogen at 200 ° C. for 5 minutes, and further heated in vacuum at 425 ° C. for 1 hour, A colorless and transparent film was formed. The evaluation results of the composition and film are shown in Table 1.

4.2.5. Comparative Example 3
In a quartz separable flask substituted with nitrogen, add 121.8 g of methyltrimethoxysilane (component (B)), 101.3 g of tetramethoxysilane (component (A)), and 632.1 g of propylene glycol monoethyl ether, After heating this to 60 ° C. in a water bath, 2.0 g of 20% oxalic acid aqueous solution and 142.9 g of ultrapure water were added and stirred at 60 ° C. for 5 hours. The liquid was concentrated under reduced pressure to a total solution amount of 500 g to a solid content of 20%, diluted with propylene glycol monoethyl ether to a solid content of 10%, and a composition containing a hydrolysis condensate was obtained. Obtained.

  The obtained composition was applied onto an 8-inch silicon wafer by spin coating, heated in the atmosphere at 80 ° C. for 5 minutes, then under nitrogen at 200 ° C. for 5 minutes, and further heated in vacuum at 425 ° C. for 1 hour, A colorless and transparent film was formed. The evaluation results of the composition and film are shown in Table 1.

4.2.6. Example 3
In a quartz separable flask substituted with nitrogen, 81.2 g of methyltrimethoxysilane (component (B)), 160.9 g of bis (triethoxysilyl) ethane (component (A)), and 215.3 g of ethanol were added. After heating this to 60 ° C. in a water bath, 275.16 g of 20% tetrapropylammonium hydroxide aqueous solution and 267.5 g of ultrapure water were added and stirred at 60 ° C. for 1 hour. After cooling to 10 ° C. or less in an ice bath, 157.1 g of 20% maleic acid aqueous solution was added to neutralize, 200 g of diethyl ether and 1000 g of propylene glycol monoethyl ether were added thereto, and then 0.2% maleic acid aqueous solution was added. Extraction processing was performed using 1000 g. This organic phase is concentrated under reduced pressure to a total solution amount of 500 g to a solid content of 20%, diluted to 10% solids with propylene glycol monoethyl ether, and a composition containing a hydrolysis condensate Got.

  The obtained composition was applied onto an 8-inch silicon wafer by spin coating, heated in the atmosphere at 80 ° C. for 5 minutes, then under nitrogen at 200 ° C. for 5 minutes, and further heated in vacuum at 425 ° C. for 1 hour, A colorless and transparent film was formed. The evaluation results of the composition and film are shown in Table 1.

4.2.7. Comparative Example 4
In a quartz separable flask substituted with nitrogen, 81.2 g of methyltrimethoxysilane (component (B)), 160.9 g of bis (triethoxysilyl) ethane (component (A)), and 215.3 g of ethanol were added. After heating this to 60 ° C. in a water bath, 275.16 g of 20% tetrapropylammonium hydroxide aqueous solution and 267.5 g of ultrapure water were added and stirred at 60 ° C. for 1 hour. After cooling to 10 ° C. or lower in an ice bath, 157.1 g of a 20% maleic acid aqueous solution was added to neutralize, 200 g of diethyl ether and 1000 g of propylene glycol monoethyl ether were added thereto, and then 1000 g of ultrapure water was used. An extraction process was performed. This organic phase is concentrated under reduced pressure to a total solution amount of 500 g to a solid content of 20%, diluted to 10% solids with propylene glycol monoethyl ether, and a composition containing a hydrolysis condensate Got.

  The obtained composition was applied onto an 8-inch silicon wafer by spin coating, heated in the atmosphere at 80 ° C. for 5 minutes, then under nitrogen at 200 ° C. for 5 minutes, and further heated in vacuum at 425 ° C. for 1 hour, A colorless and transparent film was formed. The evaluation results of the composition and film are shown in Table 1.

4.2.8. Example 4
Into a quartz-separable flask substituted with nitrogen, 255.3 g of tetramethoxysilane (component (A)) and 674.1 g of propylene glycol monomethyl ether were added and heated to 60 ° C. in a water bath. Add 3.2 g and 69.4 g of ultrapure water and stir at 60 ° C. for 5 hours. Here, 60.0 g of polyoxyethylene polyoxypropylene block copolymer (trade name “PE-61”, manufactured by Sanyo Chemical Industries) In addition, a composition containing a hydrolysis condensate was obtained.

  The obtained composition was applied onto an 8-inch silicon wafer by spin coating, heated in the atmosphere at 80 ° C. for 5 minutes, then under nitrogen at 200 ° C. for 5 minutes, and further heated in vacuum at 425 ° C. for 1 hour, A colorless and transparent film was formed. The evaluation results of the composition and film are shown in Table 1.

4.2.9. Comparative Example 5
In a quartz-separable flask substituted with nitrogen, 255.3 g of tetramethoxysilane (component (A)) and 566.1 g of propylene glycol monomethyl ether were added, heated to 60 ° C. in a water bath, and then 20% aqueous maleic acid solution. Add 3.2 g and 177.4 g of ultrapure water and stir at 60 ° C. for 5 hours. Here, 60.0 g of polyoxyethylene polyoxypropylene block copolymer (trade name “PE-61”, manufactured by Sanyo Chemical Industries) In addition, a composition containing a hydrolysis condensate was obtained.

  The obtained composition was applied onto an 8-inch silicon wafer by spin coating, heated in the atmosphere at 80 ° C. for 5 minutes, then under nitrogen at 200 ° C. for 5 minutes, and further heated in vacuum at 425 ° C. for 1 hour, A colorless and transparent film was formed. The evaluation results of the composition and film are shown in Table 1.

4.3. Discussion of Results (1) In Example 1 and Example 2, oxalic acid having a pH suitable for silica sol is used as a catalyst for the hydrolysis condensation reaction. Further, Example 1 controls the amount of water by concentration, and Example 2 controls the amount of water by reducing the amount of water charged. The compositions obtained in Example 1 and Example 2 are excellent in storage stability, and the films obtained in Example 1 and Example 2 have a high elastic modulus while having a relative dielectric constant of 2.9 or less. Have

  On the other hand, the composition obtained in Comparative Example 1 has a high water content, and in Comparative Example 2, since nitric acid was used as a catalyst for the hydrolysis condensation reaction, the pH of the obtained composition was low. As a result, the storage stability was poor. Further, although the composition obtained in Comparative Example 3 is controlled in both pH and water content, the ratio of methyltrimethoxysilane (component (B)) in the silane monomer exceeds 50 mol%. The film obtained from the composition obtained in 1 had a low elastic modulus.

  (2) Both Example 3 and Comparative Example 4 use a basic compound as a catalyst for the hydrolysis condensation reaction, and are the same until neutralization with an organic acid after the reaction. In Example 3, an aqueous solution of maleic acid was used, and in Comparative Example 4, ultrapure water was used. For this reason, the composition obtained in Example 3 has an appropriate pH of around 4, whereas the composition obtained in Comparative Example 4 has a pH exceeding 5. For this reason, the composition obtained in Example 3 is excellent in storage stability, whereas the composition obtained in Comparative Example 4 has low storage stability.

  (3) Example 4 and Comparative Example 5 correspond to the relationship between Example 2 and Comparative Example 1 in that the amount of moisture used during hydrolysis condensation is different. In Example 4, the amount of water used at the time of hydrolytic condensation is smaller than that in Comparative Example 5. For this reason, the composition obtained in Example 4 is superior in storage stability as compared with the composition obtained in Comparative Example 5.

  Since each of the compositions obtained in Example 4 and Comparative Example 5 contains an organic polymer for pore formation, the obtained film had a low relative dielectric constant. This indicates that the relative dielectric constant of the obtained film can be lowered by adding an organic polymer to the composition.

  As described above, the composition for forming an insulating film obtained by the present invention is excellent in storage stability. In addition, the silica-based film obtained by the present invention is suitable as an interlayer insulating film for semiconductor elements and the like because of its excellent mechanical strength and low relative dielectric constant.

Claims (5)

(A) component; 50-100 mol% of at least 1 sort (s) of silane compounds chosen from the group of the compound represented by the compound represented by the following general formula (1), and the following general formula (2), (B) A component; a hydrolytic condensate obtained by hydrolytic condensation of 0 to 50 mol% of another hydrolyzable silane compound, and an organic solvent,
A composition for forming an insulating film having a pH in the range of 3.0 to 5.0 and a water content of 2% by mass 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 are the same or different and each represents a monovalent organic group, a and b are the same or different and represent 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.) In claim 1,
The component (B) is a composition for forming an insulating film, which is a compound represented by the following general formula (3).
R ⁷ _d Si (OR ⁸ ) _4-d (3)
(Wherein R ⁷ represents a hydrogen atom, a fluorine atom, or a monovalent organic group, R ⁸ represents a monovalent organic group, and d represents an integer of 1 to 3) In claim 1 or 2,
An insulating film forming composition further comprising an organic polymer as a film hollow hole forming agent.   4. 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 4.