JP2010043190A - Composition for forming insulating film, and silica-based film and its formation method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for forming insulating films, which can suitably be used for semiconductor elements for which high integration and multilayer formation are desired, and the like, has excellent storage stability and low relative dielectric constant, and can be used for forming insulating films excellent in mechanical strengths, to provide a silica-based film, and to provide a method for forming the same. <P>SOLUTION: There is provided the composition for forming insulating films, comprising an organic solvent and a polymer obtained by hydrolysis-condensing at least one silane compound selected from the group consisting of a compound represented by following general formula (1): Si(OR<SP>1</SP>)<SB>4</SB>(wherein, R<SP>1</SP>is a monovalent organic group) and a compound represented by following general formula (2): R<SP>2</SP><SB>a</SB>(R<SP>3</SP>O)<SB>3a-</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>äwherein, R<SP>2</SP>to R<SP>5</SP>are the same or different and each a monovalent organic group; (a) and (b) are the same or different and each number of 0 to 1; R<SP>6</SP>is an oxygen atom, phenylene or -(CH<SB>2</SB>)<SB>m</SB>- [(m) is an integer of 1 to 6]; (c) is 0 or 1}, wherein, the polymer contains silanol groups; and the number of hydroxy groups contained in the silanol groups is 70 to 130% based on the number of silicon atoms in the polymer. <P>COPYRIGHT: (C)2010,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 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, there is almost no knowledge so far regarding sufficiently controlling the amount of silanol groups (—SiOH) of these silane compounds in the sol state.

  When the amount of silanol groups in the sol is large, the bond between the sols generated when the coating film containing the sol is baked increases, so that the mechanical strength of the resulting film can be improved, but it can be crosslinked. Since the number of functional groups is large, the condensation reaction between the sol particles is likely to occur, so that the storage stability of the sol may be lowered.

On the other hand, when the amount of silanol groups in the sol is small, the number of functional groups that can be crosslinked is reduced, so that the storage stability of the composition is improved, while the gelation temperature during firing is generally Since the film tends to increase, the film shrinkage from pre-baking to main baking tends to be large, and the mechanical strength of the resulting film is reduced because there are few bonds between the sols when the coating film containing the sol is baked. There is a risk.
US Pat. No. 6,495,264

  In view of the above background, development of an organic silica sol for forming an insulating film having excellent storage stability, a low relative dielectric constant, and excellent mechanical strength has been demanded.

  INDUSTRIAL APPLICABILITY The present invention can be suitably used in semiconductor elements and the like that are desired to be highly integrated and multi-layered, and can form an insulating film having excellent storage stability, low dielectric constant, and excellent mechanical strength. An insulating film-forming composition that can be used for the present invention is provided.

  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 polymer obtained by hydrolytic condensation of a compound represented by the following general formula (1) and at least one silane compound selected from the group of compounds represented by the following general formula (2), an organic solvent, Including,
The polymer contains silanol groups;
The composition for insulating film formation whose number of the hydroxyl groups contained in the said silanol group is 70 to 130% with respect to the number of the silicon atoms in the said polymer.
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 said insulating film formation composition, the usage-amount of the compound represented by the said General formula (2) can be 50-100 mol% of the total amount of the said silane compound in the said hydrolysis condensation.

In the composition for forming an insulating film, the silane compound may further include 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 polymer contains a silanol group, and the number of hydroxyl groups contained in the silanol group is 70 to 130% with respect to the number of silicon atoms in the polymer. In addition to excellent storage stability, the film shrinkage rate during firing of the coating film is small, so that an insulating film having excellent mechanical strength and a small relative dielectric constant can be formed.

  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 specifically described.

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. Hydrolysis condensation of at least one silane compound selected from the group of compounds represented by formula (2) (hereinafter also referred to as “compound 2”) (hereinafter also referred to simply as “silane compound”). The obtained polymer (hydrolysis condensate) and an organic solvent,
The polymer contains silanol groups, and the number of hydroxyl groups contained in the silanol groups is 70 to 130% with respect to the number of silicon atoms in the polymer.
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.)
The number of hydroxyl groups contained in the silanol group in the polymer and the number of silicon atoms in the polymer can be calculated by the area ratio of the Si-containing structural units obtained by waveform separation analysis of the ²⁹ Si NMR spectrum for the polymer, More specifically, it can be calculated by the method shown in the embodiment of the present application.

  In the composition for forming an insulating film according to the present embodiment, when the number of hydroxyl groups contained in the silanol group in the polymer is less than 70% with respect to the number of silicon atoms in the polymer, the film shrinkage rate is increased. The mechanical strength may be inferior, while if it exceeds 130%, the storage stability may be inferior.

  The number of hydroxyl groups contained in the silanol group in the polymer is appropriately set, for example, the ratio of compound 1 and compound 2 in the silane compound, reaction time, reaction temperature, type of catalyst used, presence or absence of a concentration step after hydrolysis condensation, etc. It can be controlled by doing.

  Moreover, in the composition for forming an insulating film according to this embodiment, the number of hydroxyl groups contained in the silanol group in the polymer is more preferably 80 to 120% with respect to the number of silicon atoms in the polymer.

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

1.1. Polymer (hydrolysis condensate)
As described above, the polymer is mainly composed of a tetrafunctional or higher functional silane compound (compound 1 and / or compound 2). A polymer having a Si—O—Si bond can be obtained by hydrolytic condensation of a silane compound. Moreover, it is preferable that a silane compound contains 50-100 mol% (raw material ratio) of compound 2 of the total amount of a silane compound, It is more preferable to contain 65-100 mol%, 85 mol% -100 mol% is contained. More preferably.

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.

1.1.2. 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.

1.1.3. Compound 3
The silane compound may further contain, for example, 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).

  The silane compound may not contain the compound 3, but when the silane compound contains the compound 3, the silane compound preferably contains 1 to 50 mol% (raw material ratio) of the compound 3 based on the total amount of the silane compound. It is more preferable to contain -45 mol%, and it is further more preferable to contain 10 mol%-40 mol%.

  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.

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

1.1.4-1. Metal Chelate Compound A metal chelate compound that 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, 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.

1.1.4-2. Acidic compounds Examples of acidic compounds that can be used as a catalyst include organic acids and inorganic acids. 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.

1.1.4-3. Basic compounds Examples of basic compounds that can be used as a catalyst include methanolamine, ethanolamine, propanolamine, butanolamine, N-methylmethanolamine, N-ethylmethanolamine, N-propylmethanolamine, and N-butylmethanol. Amine, N-methylethanolamine, N-ethylethanolamine, N-propylethanolamine, N-butylethanolamine, N-methylpropanolamine, N-ethylpropanolamine, N-propylpropanolamine, N-butylpropanolamine, N-methylbutanolamine, N-ethylbutanolamine, N-propylbutanolamine, N-butylbutanolamine, N, N-dimethylmethanolamine, N, N-diethylmethanolamine N, N-dipropylmethanolamine, N, N-dibutylmethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N-dipropylethanolamine, N, N-dibutylethanolamine 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-ethyldiethano Amine, 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) methanol 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, ethyl Ruamine, propylamine, butylamine, N, N-dimethylamine, N, N-diethylamine, N, N-dipropylamine, N, N-dibutylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tetramethylammonium hydro Oxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetramethylethylenediamine, tetraethylethylenediamine, tetrapropylethylenediamine, tetrabutylethylenediamine, methylaminomethylamine, methylaminoethylamine, methylaminopropyl Amine, methylaminobutylamine, ethylaminomethylamine, ethylaminoethylamine, ethyl Aminopropylamine, ethylaminobutylamine, propylaminomethylamine, propylaminoethylamine, propylaminopropylamine, propylaminobutylamine, butylaminomethylamine, butylaminoethylamine, butylaminopropylamine, butylaminobutylamine, pyridine, pyrrole, piperazine, Examples include pyrrolidine, piperidine, picoline, morpholine, methylmorpholine, diazabicycloocrane, diazabicyclononane, diazabicycloundecene, ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, etc. it can.

  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, or 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 a catalyst, 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 an acidic compound used here, the acidic compound illustrated as a catalyst can be used, and it is more preferable to use an organic acid.

1.1.5. Organic Solvent Examples of organic solvents that can be used in producing a polymer (hydrolysis condensate) include, for example, methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t- Alcohol solvents such as butanol; ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2 Polyhydric alcohol solvents such as 1,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethyl Polyhydric alcohol partial ether solvents such as lenglycol 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- -Butyl ketone, methyl-n-hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonyl Examples include ketone solvents such as acetone and 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, polyoxyethylene alkylphenyl ether, polyoxyethylene sterol ether, polyoxyethylene lanolin derivative, ethylene oxide of alkylphenol formalin condensate Derivatives, ether type compounds such as polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene fatty acid Ether ester type compounds such as alkanolamide sulfate, polyethylene glycol 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 produced.

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. Quantification method of silanol group Using a BRUKER AVANCE 500 type (manufactured by Bruker), a ²⁹ Si NMR spectrum (100 MHz) of a polymer (hydrolysis condensate) was measured (solvent: heavy benzene). In this measurement, each peak is attributed to the silicon atoms (T1 to T3 and Q1 to Q4) shown in Table 1. The number of silanols relative to the total number of silicon atoms (hereinafter also referred to as “ratio X”) can be quantified by determining the area ratio of each silicon atom after performing waveform separation analysis. That is, assuming that the area ratios of silicon atoms T1 to T3 and Q1 to Q4 are ST1 to ST3 and SQ1 to SQ4, respectively, the total number of silicon atoms is the sum of ST1 to ST3 and SQ1 to SQ4 (ST1 + ST2 + ST3 + SQ1 + SQ2 + SQ3 + SQ4), and the ratio X is an equation {X = (2 × ST1 + 1 × ST2 + 0 × ST3 + 3 × SQ1 + 2 × SQ2 + 3 × SQ3 + 0 × SQ4) / (ST1 + ST2 + ST3 + SQ1 + SQ2 + SQ3 + SQ4)}.

4.1.2. Storage stability After preparing a film-forming composition having a solid content concentration of 10%, the composition was immediately put in a 25 ° C. storage and stored for one month. The kinematic viscosity of the composition after storage was measured using an Ubbelohde viscosity tube 532-13 (manufactured by Schott). The storage stability was evaluated as follows according to the change in kinematic viscosity before and after storage.

A: Kinematic viscosity increase rate before and after storage is less than 5% B: Kinematic viscosity increase rate before and after storage is 5% or more 4.1.3. Film Shrinkage 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 heated on a hot plate at 90 ° C. for 3 minutes. Next, it was dried at 200 ° C. for 3 minutes in a nitrogen atmosphere, and further fired for 1 hour in a vertical furnace at 420 ° C. under a reduced pressure of 50 mTorr (vacuum atmosphere) to obtain a silica-based film. At this time, the film thickness before and after the film baking was measured, and the film shrinkage rate was obtained by the following formula.

Film shrinkage rate (%) = [1− (film thickness after firing) / (film thickness before firing)] × 100 (%)
4.1.4. Relative permittivity An aluminum electrode pattern was formed by vapor deposition on a silicon wafer on which a silica-based film was obtained, which was obtained by measuring the film shrinkage rate, to prepare a sample for measuring the relative permittivity. With respect to the sample, the relative dielectric constant of the film at 200 ° C. was measured at a frequency of 100 kHz by the CV method using an HP 16451B electrode and an HP4284A precision LCR meter manufactured by Agilent.

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

4.1.6. 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.

4.2. Production of film-forming composition and film formation 4.2.1. Example 1
In a nitrogen-separated quartz separable flask, 536.3 g of 1,2-bis (triethoxysilyl) ethane and 217.7 g of propylene glycol monoethyl ether were added and heated to 60 ° C. in a water bath. 3.4 g of oxalic acid aqueous solution and 242.6 g of ultrapure water were added and stirred at 60 ° C. for 1 hour. This liquid was diluted with propylene glycol monoethyl ether to a solid content of 10% to obtain a composition containing a polymer (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 2.

4.2.2. Comparative Example 1
In a nitrogen-substituted quartz separable flask, 268.2 g of 1,2-bis (triethoxysilyl) ethane and 608.8 g of propylene glycol monoethyl ether were added, and after heating to 40 ° C. in a water bath, 20% 1.7 g of oxalic acid aqueous solution and 121.3 g of ultrapure water were added and stirred at 40 ° C. for 1 hour to obtain a composition containing a polymer (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 2.

4.2.3. Comparative Example 2
In a nitrogen-separated quartz separable flask, 536.3 g of 1,2-bis (triethoxysilyl) ethane and 217.7 g of propylene glycol monoethyl ether were added and heated to 60 ° C. in a water bath. 3.4 g of oxalic acid aqueous solution and 242.6 g of ultrapure water were added and stirred at 60 ° C. for 4 hours. This liquid was diluted with propylene glycol monoethyl ether to a solid content of 10% to obtain a composition containing a polymer (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 2.

4.2.4. Example 2
6 g of a polyoxyethylene polyoxypropylene block copolymer (trade name “PE-61”, manufactured by Sanyo Chemical Industries) was added to 100 g of the composition obtained in Example 1, to obtain a composition of Example 2. 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 2.

4.2.5. Comparative Example 3
6 g of a polyoxyethylene polyoxypropylene block copolymer (trade name “PE-61”, manufactured by Sanyo Chemical Industries) was added to 100 g of the composition obtained in Comparative Example 1 to obtain a composition of Comparative Example 3. 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 2.

4.2.6. Comparative Example 4
6 g of a polyoxyethylene polyoxypropylene block copolymer (trade name “PE-61”, manufactured by Sanyo Chemical Industries) was added to 100 g of the composition obtained in Comparative Example 2 to obtain a composition of Comparative Example 4. 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 2.

4.2.7. Example 3
In a nitrogen-substituted quartz separable flask, 60.9 g of methyltrimethoxysilane, 201.7 g of bis (triethoxysilyl) methane and 604.8 g of propylene glycol monomethyl ether were added, and the internal temperature was controlled at 30 ° C. Then, 1.9 g of 20% nitric acid aqueous solution and 130.8 g of ultrapure water were added and stirred at 30 ° C. for 1 hour to obtain a composition containing a polymer (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 2.

4.2.8. Comparative Example 5
In a nitrogen-substituted quartz separable flask, 60.9 g of methyltrimethoxysilane, 201.7 g of bis (triethoxysilyl) methane and 604.8 g of propylene glycol monomethyl ether were added, and the internal temperature was controlled at 30 ° C. Then, 1.9 g of 20% nitric acid aqueous solution and 130.8 g of ultrapure water were added and stirred at 30 ° C. for 1 hour. This liquid was once concentrated to a solid content of 20% with a rotary evaporator, and then this liquid was diluted with propylene glycol monomethyl ether to a solid content of 10% to obtain a composition containing a polymer (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 2.

4.2.9. Example 4
In a quartz separable flask substituted with nitrogen, 142.1 g of methyltrimethoxysilane, 86.4 g of bis (triethoxysilyl) methane and 645.4 g of propylene glycol monomethyl ether were added, and the internal temperature was controlled at 30 ° C. Then, 1.8 g of 20% nitric acid aqueous solution and 124.3 g of ultrapure water were added and stirred at 30 ° C. for 1 hour to obtain a composition containing a polymer (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 2.

4.2.10. Example 5
In a quartz separable flask substituted with nitrogen, in a mixed solution of 1.59 g of tri-i-propoxy mono (acetylacetonato) titanium, 104.4 g of ultrapure water and 677.0 g of propylene glycol monoethyl ether, 1 , 2-bis (methyldiethoxysilyl) ethane (140.9 g) and tetramethoxysilane (76.0 g) were added and reacted at 60 ° C. for 3 hours to obtain a composition containing a polymer (hydrolysis condensate).

4.2.11. Example 6
In a quartz separable flask purged with nitrogen, in a mixed solution of 1.12 g of tri-i-propoxy mono (acetylacetonate) titanium, 147.2 g of ultrapure water, 613.9 g of propylene glycol monoethyl ether, 1 , 2-bis (methyldiethoxysilyl) ethane (60.4 g) and tetramethoxysilane (177.7 g) were added and reacted at 60 ° C. for 3 hours to obtain a composition containing a polymer (hydrolysis condensate).

4.2.12. Comparative Example 6
In a quartz separable flask substituted with nitrogen, in a mixed solution of 1.59 g of tri-i-propoxy mono (acetylacetonato) titanium, 104.4 g of ultrapure water and 677.0 g of propylene glycol monoethyl ether, 1 , 2-bis (methyldiethoxysilyl) ethane (140.9 g) and tetramethoxysilane (76.0 g) were added and reacted at 60 ° C. for 3 hours. This was once concentrated with a rotary evaporator to a solid content concentration of 20%, and again diluted with propylene glycol monoethyl ether to a solid content concentration of 10% to obtain a composition containing a polymer (hydrolysis condensate).

4.2.13. Comparative Example 7
In a quartz separable flask purged with nitrogen, in a mixed solution of 1.12 g of tri-i-propoxy mono (acetylacetonate) titanium, 147.2 g of ultrapure water, 613.9 g of propylene glycol monoethyl ether, 1 , 2-bis (methyldiethoxysilyl) ethane (60.4 g) and tetramethoxysilane (177.7 g) were added and reacted at 60 ° C. for 3 hours. This was once concentrated with a rotary evaporator to a solid content concentration of 20%, and again diluted with propylene glycol monoethyl ether to a solid content concentration of 10% to obtain a composition containing a polymer (hydrolysis condensate).

4.2.14. Comparative Example 8
In a quartz-separable flask substituted with nitrogen, tetramethoxysilane 38.0 g, 1,2-bis (methyldiethoxysilyl) ethane 70.5 g, and ethanol 781.3 g were added, and tetrapropylammonium was added to the mixed solution. 99.4 g of a 40% aqueous solution of hydroxide and 10.8 g of ultrapure water were added and reacted at 60 ° C. for 1 hour. Next, 170.2 g of a 20% aqueous solution of maleic acid was added for neutralization to complete the reaction. 500 g of propylene glycol monoethyl ether was added thereto, and the mixture was concentrated to a solid content concentration of 20% using a rotary evaporator. Further, this was diluted with propylene glycol monoethyl ether to a solid content concentration of 10% to obtain a composition containing a polymer (hydrolysis condensate).

4.3. Discussion of results (1) In Example 1, the number of silanol groups relative to the number of silicon atoms is in the range of 70 to 130%, the storage stability of the composition is good, the film shrinkage rate is small, and It can be seen that the balance between the elastic modulus and the relative dielectric constant of the insulating film is excellent. On the other hand, in Comparative Example 1, the number of silanol groups relative to the number of silicon atoms exceeds 130%, and the low storage stability of the film is inferior. In Comparative Example 2, the number of silanol groups relative to the number of silicon atoms is less than 70%, the film shrinkage rate is high, and the balance between the elastic modulus and relative dielectric constant of the film is inferior to that of Example 1. .

  (2) In addition, Example 2 and Comparative Examples 3 and 4 have the same combination as Example 1 and Comparative Examples 1 and 2, and for the purpose of reducing the relative dielectric constant of the film, a membrane hollow hole forming agent (organic polymer) ) In the composition. Example 2 and Comparative Examples 3 and 4 have the same tendency as Example 1 and Comparative Examples 1 and 2 in terms of storage stability, film shrinkage, and the balance between the elastic modulus and relative dielectric constant of the film. More interestingly, the relative dielectric constant of the film was lower in Example 2 and Comparative Example 3 than in Comparative Example 4 in spite of adding the same amount of the same organic polymer. The relative dielectric constant of the film of Comparative Example 3 was low because, as in Comparative Example 3, in the case of a polymer in which the number of silanol groups relative to the number of silicon atoms exceeds 130%, the temperature required for gelation is Since the number of silanol groups relative to the number is lower than that of a polymer having 70 to 130%, the skeleton solidifies before the organic polymer volatilizes or decomposes at the time of firing, and the space where the organic polymer disappears remains as voids. Therefore, it is considered that the relative dielectric constant is lowered.

  (3) Example 3 and Comparative Example 5 have the same raw material composition and reaction conditions. In Comparative Example 5, since the concentration operation was performed after the reaction, condensation of silanol groups proceeded. As a result, the number of silanol groups contained in the polymer in the composition was less than 70%. Thereby, in the comparative example 5, it is thought that the film shrinkage ratio and the balance between the elastic modulus of the film and the relative dielectric constant are inferior to those of the film of Example 3. Example 5 is an example in which the composition ratio of methyltrimethoxysilane and bis (triethoxysilyl) methane in Example 3 was changed. It can be seen that the film of Example 3 has a better balance between the elastic modulus and relative dielectric constant of the film than the film of Example 5. This indicates that the use of compound 2 as a raw material tends to improve the balance between the elastic modulus and relative dielectric constant of the film.

  (4) Example 5 and Comparative Example 6, and Example 6 and Comparative Example 7 were the same raw material composition and the same reaction conditions, respectively. In Comparative Example 6 and Comparative Example 7, the post-reaction concentration operation was performed. Thus, the number of silanol groups with respect to the number of silicon atoms is less than 70%, and as in the previous examples, the balance between the film shrinkage ratio and the elastic modulus of the film and the relative dielectric constant is shown in Example 5 and Example 6. Each is inferior. In Example 5, the raw material (compound 2) having a silicon-carbon chain-silicon skeleton was used as the main raw material, and the balance between the elastic modulus and relative dielectric constant of the insulating film was even better than in Example 6. It has become. From this result, it can be seen that the use of compound 2 allows more efficient construction of a crosslinked structure during polymer synthesis.

  (5) Furthermore, in Example 5 and Comparative Example 8, it is understood that the composition of the raw materials used is the same and the molecular weight of the polymer is the same, but the amount of silanol groups is different. In addition, as described above, the film of Example 5 having a large number of silanol groups has a lower film shrinkage rate than the film of Comparative Example 8, and the balance between the elastic modulus of the insulating film and the relative dielectric constant was also carried out. It can be seen that the film of Example 5 is superior to the film of Comparative Example 8.

  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 has a low film shrinkage rate from pre-baking to baking, and further has an excellent balance between elastic modulus and relative dielectric constant. It is suitable as.

  This is the end of the description of the embodiment according to the present invention. The present invention includes configurations that are substantially the same as the configurations described in the embodiments (for example, configurations that have the same functions, methods, and results, or configurations that have the same purposes and results). In addition, the invention includes a configuration in which a non-essential part of the configuration described in the embodiment is replaced. In addition, the present invention includes a configuration that exhibits the same operational effects as the configuration described in the embodiment or a configuration that can achieve the same object. Further, the invention includes a configuration in which a known technique is added to the configuration described in the embodiment.

Claims (6)

A polymer obtained by hydrolytic condensation of a compound represented by the following general formula (1) and at least one silane compound selected from the group of compounds represented by the following general formula (2), an organic solvent, Including,
The polymer contains silanol groups;
The composition for insulating film formation whose number of the hydroxyl groups contained in the said silanol group is 70 to 130% with respect to the number of the silicon atoms in the said polymer.
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,
In the hydrolysis condensation, the amount of the compound represented by the general formula (2) is 50 to 100 mol% of the total amount of the silane compound. In claim 1 or 2,
The said silane compound is a composition for insulating film formation which further contains the compound represented by 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 any of claims 1 to 3,
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 composition for forming an insulating film according to claim 1 to a substrate to form a coating film; and a step of subjecting the coating film to a curing treatment. Method.   A silica-based film obtained by the method for forming a silica-based film according to claim 5.