JP2006249181A - Method for producing composition for forming insulating material, composition for forming insulating material and insulating film using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for insulating materials, capable of forming insulating films having low dielectric constants and high mechanical strengths. <P>SOLUTION: The method for producing the composition used for insulating materials and comprising a compound obtained by hydrolyzing and condensing at least one silane compound selected from a compound represented by general formula (1) [X<SP>1</SP>is a hydrolysable group; R<SP>1</SP>is an alkyl, an aryl or a heterocyclic group; (n<SB>1</SB>) is an integer of 1 to 3; (m<SB>1</SB>) is an integer of ≥2; L<SP>1</SP>is a single bond or a divalent bonding group; A is a group containing a cage type structure], its hydrolysate and its condensation product in the presence of a substituted or non-substituted ammonium salt. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a composition for forming an insulating material useful for forming an insulating film and a composition for forming an insulating material obtained therefrom, and further to an insulating material having a good dielectric constant obtained by using the composition.

Cited Document 1 discloses a method for producing a composition for forming an insulating material characterized in that a conventional sol-gel reaction precursor is hydrolyzed in the presence of a nitrogen onium salt compound, and the temperature dependence of the dielectric constant is small. It has been shown that a composition for forming an insulating material capable of forming a stable film with high mechanical strength can be obtained. However, a low dielectric constant, which is an important characteristic as an interlayer insulating film, and a high mechanical strength have been desired.
Japanese Patent Laid-Open No. 2002-20687

  An object of the present invention is to provide a composition capable of forming an insulating film having a low dielectric constant and high mechanical strength.

The above object of the present invention can be achieved by the following constitution.
(1) Obtained by hydrolyzing and condensing at least one silane compound selected from the compound represented by general formula (1), its hydrolysis and its condensate in the presence of a substituted or unsubstituted ammonium salt. The manufacturing method of the composition for insulating material formation containing the compound obtained.

In General Formula (1), X ¹ represents a hydrolyzable group, R ¹ represents an alkyl group, an aryl group, or a heterocyclic group, n ₁ represents an integer of ₁ to 3, and m ₁ represents 2 or more. Represents an integer. L ¹ represents a single bond or a divalent linking group, and A represents a group containing a cage structure.
(2) The production method according to (1), wherein in formula (1), A contains a diamantyl group.
(3) The production method according to any one of (1) to (2), wherein the ammonium salt is represented by the following general formula (2).

In the general formula (2), R ^{2 to} R ⁵ each independently represents a hydrogen atom, an alkyl group, or an aryl group. n represents an integer of 1 to 3. X represents an n-valent anionic group. R ^{2 to} R ⁵ may be linked to each other to form a ring structure.
(4) A composition for forming an insulating material obtained by the method described in (1) to (3).
(5) An insulating material formed from the composition according to (4).
(6) An insulating film formed from the composition according to (5).

  By adding the general formula (2) to the compound of the general formula (1) of the present invention, a film having a low dielectric constant and excellent mechanical strength can be obtained. Further, it can be seen that the addition of the general formula (2) produces a film having higher mechanical strength in combination with a compound having a cage structure as shown in the general formula (1), and exhibits a great effect. It was.

  The composition for forming an insulating material useful for formation of the insulating film and the like of the present invention includes at least one silane compound selected from the compound represented by the general formula (1), its hydrolysis and its condensate. The compound obtained by adding the compound represented by Formula (2), hydrolyzing and condensing is contained.

In General Formula (1), X ¹ represents a hydrolyzable group, R ¹ represents an alkyl group, an aryl group, or a heterocyclic group, n ₁ represents an integer of ₁ to 3, and m ₁ represents 2 or more. Represents an integer. L ¹ represents a single bond or a divalent linking group, and A represents a group containing a cage structure.

Examples of the hydrolyzable group as X ¹ include a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, a silyloxy group, and a hydroxyl group. X ¹ is preferably a substituted or unsubstituted alkoxy group (for example, methoxy group, ethoxy group, propoxy group, butoxy group, methoxyethoxy group, etc.).

R ¹ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. Preferred examples of the alkyl group represented by R ¹ include a linear, branched or cyclic alkyl group (for example, having 1 to 2 carbon atoms).
0 alkyl group, preferably methyl group, ethyl group, isopropyl group, n-butyl group, 2-ethylhexyl group, n-decyl group, cyclopropyl group, cyclohexyl group, cyclododecyl group and the like, and R ¹ Preferred examples of the aryl group represented include substituted or unsubstituted phenyl or naphthyl groups having 6 to 20 carbon atoms, and preferred examples of the heterocyclic group represented by R ¹ include substituted or unsubstituted. Examples include substituted hetero 6-membered rings (pyridyl, morpholino group, tetrahydropyranyl, etc.), substituted or unsubstituted hetero 5-membered rings (furyl, thiophene group, 1,3-dioxolan-2-yl group, etc.), etc. .

In the case of n1 = 2 or 3, a plurality of X ¹ may be the same group or different from each other. When n1 = 1, the plurality of R ¹ may be the same group or different from each other.

L ¹ represents a single bond or a divalent linking group. Examples of the linking group include an alkylene group, an alkenylene group, an arylene group, -O-, -S-, -CO-, -NR'- (R 'is a hydrogen atom, an alkyl group or an aryl group), or 2 Examples thereof include a linking group formed by combining two or more. Of the linking groups, an alkylene group and an alkenylene group are preferable, and an ethylene group and a vinylene group are particularly preferable.

  A is a group containing a cage structure (a cage structure-containing group). A “cage structure” is a structure in which the volume is determined by a plurality of rings formed of covalently bonded atoms, and points located within the volume cannot be separated from the volume without passing through the ring. For example, an adamantane structure is considered a cage structure. In contrast, a cyclic structure having a single bridge such as norbornane (bicyclo [2,2,1] heptane) is not considered a cage structure because the ring of a single bridged cyclic compound does not define volume. .

  The cage structure is preferably composed of 10 to 30, more preferably 10 to 20, and still more preferably 14 to 20 carbon atoms. The carbon atom here does not include a linking group substituted with a cage structure or a carbon atom of the substituent. For example, 1-methyladamantane is composed of 10 carbon atoms.

  The compound having a cage structure of the present invention is preferably a saturated aliphatic hydrocarbon, and examples thereof include adamantane, diamantane, triamantane, tetramantane, dodecahedrane, etc., and particularly low dielectric constant and good resistance to coating solvents. Diamantane is preferable from the viewpoints of excellent solubility and suppression of the occurrence of defects in the insulating film.

  The cage structure in the present invention may have one or more substituents. Examples of the substituent include a halogen atom (a fluorine atom, a chloro atom, a bromine atom, or an iodine atom), a carbon number of 1 to 10. Linear, branched and cyclic alkyl groups (methyl, t-butyl, cyclopentyl, cyclohexyl, etc.), alkenyl groups having 2 to 10 carbon atoms (vinyl, propenyl, etc.), alkynyl groups having 2 to 10 carbon atoms (ethynyl, phenyl) Ethynyl etc.), C6-C20 aryl groups (phenyl, 1-naphthyl, 2-naphthyl etc.), C2-C10 acyl groups (benzoyl etc.), C6-C20 aryloxy groups (phenoxy etc.) ), Arylsulfonyl groups having 6 to 20 carbon atoms (such as phenylsulfonyl), nitro groups, cyano groups, silyl groups (triethoxysilyl, methyldiethoxysilyl, A vinyl silyl, etc.) and the like. Further preferred substituents are a fluorine atom, a bromine atom, a linear, branched or cyclic alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkynyl group having 2 to 5 carbon atoms, and a silyl group. These substituents may be further substituted with another substituent.

  The cage structure in the present invention is preferably divalent to tetravalent. More preferably, it is divalent or trivalent, and particularly preferably divalent.

  Two or more cage compounds may be linked.

  A compound represented by formula (1-1) is preferred.

(In the general formula (1-1), X ^{21 to} X ²² each independently represents a hydrolyzable group, and R ^{21 to} R ²² each independently represents an alkyl group, an aryl group, or a heterocyclic group. And n ^{21 to} n ²² represent an integer of 1 to 3.

p2 represents 0 to 2, when p2 is 0, m ²¹ represents an integer of 2 to 4, when p2 is 1, m ²¹ + m ²² represents an integer of 2 to 4, and when p2 is 2, m ²¹ + m ²² represents an integer of 2-6.

L ^{21 to} L ²² each independently represents an alkylene group, a vinylene group, an arylene group, —O—, —S—, —CO—, or —NR′— (R ′ represents a hydrogen atom, an alkyl group, or an aryl group). ) Or a divalent linking group in which these groups are combined.

In General Formula (1-1), X ^{21 to} X ²² each independently represents a hydrolyzable group, R ^{21 to} R ²² each independently represents an alkyl group, an aryl group, or a heterocyclic group, n ²¹ ~n ²² represents an integer of 1 to 3.

p2 represents 0 to 2, when p2 is 0, m ²¹ represents an integer of 2 to 4, when p2 is 1, m ²¹ + m ²² represents an integer of 2 to 4, and when p2 is 2, m ²¹ + m ²² represents an integer of 2-6.

L ^{21 to} L ²² each independently represents an alkylene group, a vinylene group, an arylene group, —O—, —S—, —CO—, or —NR′— (R ′ represents a hydrogen atom, an alkyl group, or an aryl group). ) Or a divalent linking group in which these groups are combined.

In the general formula (1-1), examples of the hydrolyzable group represented by X ^{21 to} X ²² include a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, a silyloxy group, and a hydroxyl group. X ^{21 to} X ²² are preferably an alkoxy group (for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a methoxyethoxy group) or a halogen atom. Particularly preferred are a methoxy group, an ethoxy group, and a chlorine atom.

R ^{21 to} R ²² represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. Preferable examples of the alkyl group represented by R ^{21 to} R ²² include a linear, branched or cyclic alkyl group (for example, an alkyl group having 1 to 20 carbon atoms, preferably a methyl group, an ethyl group, an isopropyl group, n -Butyl group, 2-ethylhexyl group, n-decyl group, cyclopropyl group, cyclohexyl group, cyclododecyl group, etc.), and preferred examples of the aryl group represented by R ^{21 to} R ²² include 6 carbon atoms. 20 substituted or unsubstituted phenyl group, a naphthyl group and the like, and preferred examples of the heterocyclic group represented by R ²¹ to R ²² is a substituted or unsubstituted of hetero 6-membered ring (pyridyl, morpholino Group, tetrahydropyranyl, etc.), substituted or unsubstituted hetero 5-membered rings (furyl, thiophene group, 1,3-dioxolan-2-yl group, etc.) and the like.

In the case of n ^{21 to} n ²² = 2 or 3, the plurality of X ^{21 to} X ²² may be the same group or different from each other. When n ^{21 to} n ²² = 1, the plurality of R ^{21 to} R ²² may be the same group or different from each other.

L ^{21 to} L ²² represent a divalent linking group. Examples of the linking group include an alkylene group, an alkenylene group, an arylene group, -O-, -S-, -CO-, -NR'- (R 'is a hydrogen atom, an alkyl group or an aryl group), or 2 Examples thereof include a linking group formed by combining two or more, and a linking group having 10 or less carbon atoms is preferable. Of the linking groups, an alkylene group and an alkenylene group are preferable, and an ethylene group and a vinylene group are particularly preferable.

  As the compound represented by the general formula (1-1), a compound represented by the general formula (1-2) is preferable.

(In the general formula (1-2), X ^{21 to} X ²² each independently represents a hydrolyzable group, and R ^{21 to} R ²² each independently represents an alkyl group, an aryl group, or a heterocyclic group. , N ^{21 to} n ²² each represents an integer of 1 to 3. L ^{21 to} L ²² are each independently an alkylene group, vinylene group, arylene group, —O—, —S—, —CO—, —NR ′. -(R 'represents a hydrogen atom, an alkyl group or an aryl group) or a divalent linking group obtained by combining these groups.
The compound represented by the general formula (1-1) corresponds to, for example, a hydrosilylation reaction or a halogenated adamantane in which a corresponding silane compound is added to a corresponding compound having an unsaturated group in the presence of a transition metal complex catalyst. It can be easily synthesized by reaction with Grignard reagent.

  As the compound represented by the general formula (1), a compound represented by the general formula (1-3) is preferable.

In General Formula (1-3), X ^{31 to} X ³⁴ each represent a hydrolyzable group, R ^{31 to} R ³⁴ each represent an alkyl group, an aryl group, or a heterocyclic group, and n _{31 to} n ₃₄ represent Represents an integer of 1 to 3, and m ₃₁ + m ₃₂ + m ₃₃ + m ₃₄ represents an integer of 1 to 4. L ^{31 to} L ³⁴ are each alkylene, vinylene, arylene, —O—, —S—, —CO—, —NR′— (R ′ represents a hydrogen atom, an alkyl group or an aryl group) or a combination thereof. Represents a divalent linking group.

The hydrolyzable group represented by X ^{31 to} X ³⁴ has the same meaning as that represented by X ¹ , and the preferred embodiment is also the same.

The alkyl group, aryl group or heterocyclic group represented by R ^{31 to} R ³⁴ has the same meaning as that represented by R ¹ , and the preferred embodiments are also the same.

  Although the specific example of the organosilicon compound represented by Formula (1) is given, it is not limited to these.

  Next, the compound represented by formula (2) will be described.

In the general formula (2), R ^{2 to} R ⁵ each independently represents a hydrogen atom, an alkyl group, or an aryl group. n represents an integer of 1 to 3. X represents an n-valent anionic group. R ^{2 to} R ⁵ may be linked to each other to form a ring structure. The ring structure may have a heteroatom such as N or O.

The alkyl group represented by R _{2 to} R ₅ may be linear, branched or cyclic. Preferably, it is a C1-C20 alkyl group, More preferably, it is a C1-C10 alkyl group. Particularly preferred are alkyl groups having 1 to 5 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group).

Preferable examples of the aryl group represented by R _{2 to} R ₅ are substituted or unsubstituted aryl groups having 6 to 20 carbon atoms, and particularly preferably a phenyl group or a naphthyl group.

  Anionic groups represented by X are inorganic acids (nitric acid, sulfuric acid, carbonic acid, hydrochloric acid, phosphoric acid, boric acid, etc.) or organic acids (acetic acid, adipic acid, alginic acid, benzoic acid, citric acid, phthalic acid, oxalic acid, succinic acid, etc. Acid, maleic acid, carboxylic acid such as trichloroacetic acid, methanesulfonic acid, ethanesulfonic acid, sulfonic acid such as trifluoromethanesulfonic acid benzenesulfonic acid, imides such as trifluoromethanesulfonimide, active methylene compound, active methine compound, etc.) Or a hydroxide ion.

  The anionic group represented by X is preferably a conjugate base or hydroxide ion of nitric acid, oxalic acid or maleic acid, and particularly preferably a conjugate base of nitric acid.

  The molecular weight range of the compound represented by the formula (2) is generally 80 to 500, preferably 100 to 300.

  The compound represented by Formula (2) may be synthesized by a known method, or a commercially available product may be used.

  Although the specific example of a compound represented by Formula (2) is given, it is not limited to these.

  The amount of the compound represented by the general formula (2) is preferably 0.1% by mass to 20% by mass, more preferably the total amount of the silane compound to be used such as the compound represented by the general formula (1). It is 0.2 mass%-5 mass%. That is, 0.1% by mass or more is preferable in terms of the effect of lowering the dielectric constant, and 20% by mass or less is preferable in terms of coating properties and film surface properties.

  In addition to the silane compound represented by the general formula (1), other known silicon compounds (for example, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, etc.) It may be condensed to obtain a silicon oxygen crosslinking compound.

  The amount of the other silane compound added is preferably 1 to 200 mol%, more preferably 10 to 100 mol%, based on the silane compound represented by the general formula (1). .

  Examples of other silane compounds that may be added as necessary in order to improve the film properties of the material include organosilicon compounds represented by the following general formula (A) or polymers containing them as monomers. Can do.

In general formula (A), R _a represents an alkyl group, an aryl group, or a heterocyclic group, and R _b represents a hydrogen atom, an alkyl group, an aryl group, or a silyl group. These groups may further have a substituent.

q represents an integer of 0 to 4, and when q or 4-q is 2 or more, R _a or R _b may be the same or different. In addition, the compounds may be connected to each other by a substituent of R _a or R _b to form a multimer.

Q in the general formula (A) is preferably 0 to 2, and R _b is preferably an alkyl group. Further, examples of preferable compounds when q is 0 include tetramethoxysilane (TMOS), tetraethoxysilane (TEOS) and the like, and examples of preferable compounds when q is 1 or 2 include the following compounds: Can be mentioned.

  A method for obtaining a silicon oxygen crosslinking compound by hydrolysis and condensation using a silane compound represented by the general formula (1) and, if necessary, another silane compound in combination is as follows.

  When hydrolyzing and condensing the silane compound represented by the general formula (1), the timing of adding the compound of the general formula (2) is not particularly limited, and may be added in advance before the start of the hydrolysis and condensation reaction. It may be added after the hydrolysis and condensation reaction of the general formula (1) has progressed to some extent, but is preferably added in advance.

The temperature at the time of hydrolysis and condensation of the silane compound is usually 0 ° C. to the boiling point of the reaction solution, preferably room temperature to 100 ° C. (however, the temperature not exceeding the boiling point of the reaction solution), more preferably 10 to 90. ° C. The time is an arbitrary time until immediately before the composition is gelled and loses fluidity, and is not particularly limited, but is usually 5 minutes to 200 hours, preferably 15 minutes to 40 hours.

  When hydrolyzing and condensing the silane compound, 0.5 to 150 mol of water is used per 1 mol of the total amount of the silane compound represented by the general formula (1) and, if necessary, other silane compounds. It is particularly preferable to add 1 to 100 mol of water. The amount of water to be added is preferably 0.5 mol or more from the viewpoint of crack resistance of the film, and is preferably 150 mol or less from the viewpoint of polymer precipitation and prevention of gelation during hydrolysis and condensation reactions.

  When hydrolyzing and condensing the silane compound, it is preferable to use an alkali catalyst, an acid catalyst, or a metal chelate compound.

  Examples of the alkali catalyst include sodium hydroxide, potassium hydroxide, lithium hydroxide, pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, dia Zabicyclooctane, diazabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ammonia, methylamine, ethylamine, propylamine, butylamine, Pentylamine, hexylamine, pentylamine, octylamine, nonylamine Decylamine, N, N-dimethylamine, N, N-diethylamine, N, N-dipropylamine, N, N-dibutylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, cyclohexylamine, trimethylimidine, 1- Amino-3-methylbutane, dimethylglycine, 3-amino-3-methylamine and the like can be mentioned, amines or amine salts are preferable, organic amines or organic amine salts are particularly preferable, and alkylamines and tetraalkylammonium hydroxides are preferable. Most preferred. These alkali catalysts may be used alone or in combination of two or more.

The acid catalyst is preferably an inorganic or organic proton acid. Examples of inorganic protonic acids include hydrochloric acid, sulfuric acid, hydrofluoric acid, phosphoric acids (H ₃ PO ₄ , H ₃ PO ₃ , H ₄ P ₂ O ₇ , H ₅ P ₃ O ₁₀ , metaphosphoric acid, hexafluorophosphoric acid, etc.), Examples thereof include boric acid, nitric acid, perchloric acid, tetrafluoroboric acid, hexafluoroarsenic acid, hydrobromic acid, and solid acids such as tungstophosphoric acid and tungten peroxo complex.

  Organic protonic acids include carboxylic acids (oxalic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid Gallic acid, butyric acid, melottic acid, arachidonic acid, shikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, p-aminobenzoic acid, Formic acid, malonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, succinic acid, fumaric acid, itaconic acid, mesaconic acid, citraconic acid, malic acid, glutaric acid hydrolyzate, maleic anhydride hydrolyzate, anhydrous Phthalic acid hydrolysates, trifluoroacetic acid, benzoic acid, substituted benzoic acid, etc.), phosphate esters For example, C number 1-30, phosphoric acid methyl ester, phosphoric acid propyl ester, phosphoric acid dodecyl ester, phosphoric acid phenyl ester, phosphoric acid dimethyl ester, phosphoric acid didodecyl ester, etc.), phosphorous acid esters (for example, C number 1 -30, phosphorous acid methyl ester, phosphorous acid dodecyl ester, phosphorous acid diethyl ester, phosphorous acid diisopropyl, phosphorous acid didodecyl ester, etc.), sulfonic acids (for example, C number 1-15, benzenesulfonic acid, toluene Sulfonic acid, hexafluorobenzene sulfonic acid, trifluoromethane sulfonic acid, dodecyl sulfonic acid, etc.), carboxylic acids (oxalic acid, acetic acid, trifluoroacetic acid, benzoic acid, substituted benzoic acid, etc.), imides (eg bis (trifluoromethanesulfonyl) ) Imido acid, trifluorometa Low molecular weight compounds such as sulfonyl trifluoroacetamide), phosphonic acids (for example, C 1-30, methylphosphonic acid, ethylphosphonic acid, phenylphosphonic acid, diphenylphosphonic acid, 1,5-naphthalenebisphosphonic acid, etc.), or Nafion Perfluorocarbon sulfonic acid polymers represented by the following: poly (meth) acrylates having a phosphate group in the side chain (Japanese Patent Laid-Open No. 2001-114835), sulfonated polyetheretherketone (Japanese Patent Laid-Open No. 6-93111), sulfonated poly Examples thereof include polymer compounds having a ptronic acid moiety such as ether sulfone (JP-A-10-45913) and sulfonated polysulfone (JP-A-9-245818).

  Examples of the metal chelate compound include triethoxy mono (acetylacetonato) titanium, tri-n-propoxy mono (acetylacetonato) titanium, tri-i-propoxy mono (acetylacetonato) titanium, tri-n- Butoxy mono (acetylacetonato) titanium, tri-sec-butoxy mono (acetylacetonato) titanium, tri-t-butoxy mono (acetylacetonato) titanium, diethoxybis (acetylacetonato) titanium, di- n-propoxy bis (acetylacetonato) titanium, di-i-propoxy bis (acetylacetonato) titanium, di-n-butoxy bis (acetylacetonato) titanium, di-sec-butoxy bis (acetylacetate) Natto) titanium, di-t-butoxy bi (Acetylacetonato) titanium, monoethoxy-tris (acetylacetonato) titanium, mono-n-propoxy-tris (acetylacetonato) titanium, mono-i-propoxy-tris (acetylacetonato) titanium, mono-n- Butoxy-tris (acetylacetonato) titanium, mono-sec-butoxy-tris (acetylacetonato) titanium, mono-t-butoxy-tris (acetylacetonato) titanium, tetrakis (acetylacetonato) titanium, triethoxy-mono ( Ethyl acetoacetate) titanium, tri-n-propoxy mono (ethyl acetoacetate) titanium, tri-i-propoxy mono (ethyl acetoacetate) titanium, tri-n-butoxy mono (ethyl acetoacetate) titanium, tri- se -Butoxy mono (ethyl acetoacetate) titanium, tri-t-butoxy mono (ethyl acetoacetate) titanium, diethoxy bis (ethyl acetoacetate) titanium, di-n-propoxy bis (ethyl acetoacetate) titanium, di -I-propoxy bis (ethyl acetoacetate) titanium, di-n-butoxy bis (ethyl acetoacetate) titanium, di-sec-butoxy bis (ethyl acetoacetate) titanium, di-t-butoxy bis (ethyl) Acetoacetate) titanium, monoethoxy tris (ethyl acetoacetate) titanium, mono-n-propoxy tris (ethyl acetoacetate) titanium, mono-i-propoxy tris (ethyl acetoacetate) titanium, mono-n-butoxy Tris (ethylacetoa Cetate) titanium, mono-sec-butoxy-tris (ethylacetoacetate) titanium, mono-t-butoxy-tris (ethylacetoacetate) titanium, tetrakis (ethylacetoacetate) titanium, mono (acetylacetonato) tris (ethylacetate) Titanium chelate compounds such as acetate) titanium, bis (acetylacetonato) bis (ethylacetoacetate) titanium, tris (acetylacetonato) mono (ethylacetoacetate) titanium; triethoxy mono (acetylacetonato) zirconium, tri-n -Propoxy mono (acetylacetonato) zirconium, tri-i-propoxy mono (acetylacetonato) zirconium, tri-n-butoxy mono (acetylacetonato) zirconium, tri- ec-butoxy mono (acetylacetonato) zirconium, tri-t-butoxy mono (acetylacetonato) zirconium, diethoxybis (acetylacetonato) zirconium, di-n-propoxybis (acetylacetonato) zirconium, Di-i-propoxy bis (acetylacetonato) zirconium, di-n-butoxy bis (acetylacetonato) zirconium, di-sec-butoxy bis (acetylacetonato) zirconium, di-t-butoxy bis ( Acetylacetonate) zirconium, monoethoxy-tris (acetylacetonato) zirconium, mono-n-propoxy-tris (acetylacetonato) zirconium, mono-i-propoxy-tris (acetylacetonato) zirconium , Mono-n-butoxy-tris (acetylacetonato) zirconium, mono-sec-butoxy-tris (acetylacetonato) zirconium, mono-t-butoxy-tris (acetylacetonato) zirconium, tetrakis (acetylacetonato) Zirconium, triethoxy mono (ethyl acetoacetate) zirconium, tri-n-propoxy mono (ethyl acetoacetate) zirconium, tri-i-propoxy mono (ethyl acetoacetate) zirconium, tri-n-butoxy mono (ethyl aceto) Acetate) zirconium, tri-sec-butoxy mono (ethyl acetoacetate) zirconium, tri-t-butoxy mono (ethyl acetoacetate) zirconium, diethoxy bis (ethyl aceto) Acetate) zirconium, di-n-propoxy bis (ethyl acetoacetate) zirconium, di-i-propoxy bis (ethyl acetoacetate) zirconium, di-n-butoxy bis (ethyl acetoacetate) zirconium, di-sec- Butoxy bis (ethyl acetoacetate) zirconium, di-t-butoxy bis (ethyl acetoacetate) zirconium, monoethoxy tris (ethyl acetoacetate) zirconium, mono-n-propoxy tris (ethyl acetoacetate) zirconium, mono -I-propoxy tris (ethyl acetoacetate) zirconium, mono-n-butoxy tris (ethyl acetoacetate) zirconium, mono-sec-butoxy tris (ethyl acetoacetate) zil Ni, mono-t-butoxy tris (ethyl acetoacetate) zirconium, tetrakis (ethyl acetoacetate) zirconium, mono (acetylacetonato) tris (ethylacetoacetate) zirconium, bis (acetylacetonato) bis (ethylacetoacetate) Zirconium chelate compounds such as zirconium and tris (acetylacetonate) mono (ethylacetoacetate) zirconium; Aluminum chelate compounds such as tris (acetylacetonate) aluminum and tris (ethylacetoacetate) aluminum; Includes a chelate compound of titanium or aluminum, particularly preferably a chelate compound of titanium. These metal chelate compounds may be used alone or in combination of two or more.

  The amount of the catalyst and chelate compound used is generally 0.00001 to 10 mol, preferably 0.00005 to 5 mol, relative to 1 mol of the silane compound, as a total amount. If the amount of the catalyst used is within the above range, there is little risk of polymer precipitation or gelation during the reaction.

  Thus, the hydrolyzate and condensate of the silane compound represented by the general formula (1), that is, the silicon oxygen crosslinking compound of the present invention can be prepared.

The solvent used in the reaction is not particularly limited as long as it dissolves the solute silane compound, but preferably ketones (cyclohexanone, cyclopentanone, 2-heptanone, methyl isobutyl ketone, methyl ethyl ketone, acetone, etc.), Carbonate compounds (ethylene carbonate, propylene carbonate, etc.), heterocyclic compounds (3-methyl-2-oxazolidinone, dimethylimidazolidinone, N-methylpyrrolidone, etc.), cyclic ethers (dioxane, tetrahydrofuran, etc.), chain ethers ( Diethyl ether, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, polyethylene glycol dimethyl ether, etc.), alcohols (methanol, ethanol, etc.) Isopropanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether (PGME), triethylene glycol monobutyl ether, propylene glycol monopropyl ether, triethylene glycol monomethyl ether, etc.), polyhydric alcohols (ethylene glycol, propylene) Glycol, polyethylene glycol, polypropylene glycol, glycerin, etc.), nitrile compounds (acetonitrile, glutarodinitrile, methoxyacetonitrile, propionitrile, benzonitrile, etc.), esters (ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, methoxypropion) Methyl acetate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate Propylpyruvate, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), γ-butyrolactone, phosphate ester, phosphonate ester, etc., aprotic polar substance (dimethyl sulfoxide, sulfolane) N, N-dimethylformamide, dimethylacetamide, etc.), nonpolar solvents (toluene, xylene, mesitylene, etc.), chlorinated solvents (methylene dichloride, ethylene dichloride, etc.), diisopropylbenzene, water and the like can be used.

  Among these, alcohols such as propylene glycol monopropyl ether and propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (PGMEA), esters such as γ-butyrolactone, carbonates such as ethylene carbonate, ketones such as cyclohexanone, non- Protic polar substances, cyclic ethers such as tetrahydrofuran, nonpolar solvents, and water are preferred. These may be used alone or in combination of two or more.

Among these, preferable solvents include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 2-heptanone, cyclohexanone, γ-butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl. Ether, propylene glycol monoethyl ether, ethylene carbonate, butyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, N-methylpyrrolidone, N, N-dimethylformamide, tetrahydrofuran, methyl isobutyl ketone, xylene, Mention may be made of mesitylene and diisopropylbenzene.
〔Composition〕
The composition containing the silicon oxygen crosslinking compound of the present invention usually contains at least one of the silane compound itself represented by the general formula (1), the hydrolyzate of the silane compound prepared above, and the condensate. If necessary, it is prepared by dissolving in a solvent such as an organic solvent or water exemplified as a solvent used for hydrolysis and condensation.

  The total solid content concentration of the composition of the present invention is preferably 2 to 30% by mass, and is appropriately adjusted according to the purpose of use. When the total solid content concentration of the composition is 2 to 30% by mass, the film thickness of the coating film is in an appropriate range, and the storage stability of the composition is more excellent.

  A good insulating material can be formed by applying, drying, and preferably heating the composition of the present invention. In particular, a good insulating film can be provided.

When the composition of the present invention is applied to a substrate such as a silicon wafer, SiO ₂ wafer, or SiN wafer, a coating means such as spin coating, dipping method, roll coating method, spray method or the like is used.

  In this case, as a dry film thickness, it is possible to form a coating film having a thickness of about 0.05 to 1.5 μm by one coating and a thickness of about 0.1 to 3 μm by two coatings. Thereafter, it is dried at room temperature, or heated at a temperature of about 80 to 600 ° C., usually for about 5 to 240 minutes, to form an insulating film of vitreous or giant polymer or a mixture thereof. As a heating method at this time, a hot plate, an oven, a furnace, or the like can be used, and a heating atmosphere is performed in the air, a nitrogen atmosphere, an argon atmosphere, a vacuum, a reduced pressure with a controlled oxygen concentration, or the like. Can do.

  More specifically, the composition of the present invention is applied onto a substrate (usually a substrate having metal wiring) by, for example, a spin coating method, and a first heat treatment is performed at a temperature of 300 ° C. or lower to remove the solvent. While drying, the siloxane contained in the composition is crosslinked, and then a second heat treatment (annealing) at a temperature higher than 300 ° C. and lower than 450 ° C. (preferably 330 to 400 ° C.), generally for 1 minute to 10 hours. ), A low dielectric constant insulating film can be formed.

  A pore forming agent such as a thermally decomposable compound may be added to the composition of the present invention. Examples of the pore forming agent include pore generators described in JP-T-2002-530505.

  On the insulating film formed of the composition of the present invention, another insulating film such as a silicon oxide film may be formed by, for example, a vapor deposition method. This is because the insulating film formed according to the present invention is effective in blocking the outside air and suppressing the reduction of hydrogen and fluorine remaining in the film. In addition, this other insulating film is also effective in preventing the insulating film according to the present invention from being damaged by processing in a subsequent process (for example, processing such as planarization by CMP).

The present invention will be described in more detail with reference to examples. In addition, this invention is not limited by the following Example.
[Example 1]
3.6 g of Compound 1-1 and 474 mg of a 2.4% aqueous solution of Compound 2-1 were dissolved in 17.8 g of propylene glycol monomethyl ether (PGME). Next, an aqueous solution prepared by dissolving 10.6 mg of 70% nitric acid solution in 757 mg of water was added dropwise, and the reaction solution was stirred at room temperature for 5 hours. Thereafter, stirring was stopped, and the solution was concentrated under reduced pressure to remove low-boiling substances and water, followed by further filtration. A coating solution was prepared by adding a solvent having the same mass as the filtrate.
[Example 2]
3.5 g of Compound 1-5 and 468 mg of a 2.4% aqueous solution of Compound 2-1 were dissolved in 17.4 g of propylene glycol monomethyl ether (PGME). Next, an aqueous solution in which 10.4 mg of 70% nitric acid aqueous solution was dissolved in 747 mg of water was dropped, and the reaction solution was stirred at room temperature for 5 hours. Thereafter, stirring was stopped, and the solution was concentrated under reduced pressure to remove low-boiling substances and water, followed by further filtration. A coating solution was prepared by adding a solvent having the same mass as the filtrate.
Example 3
3.2 g of Compound 1-7 and 478 mg of 2.4% aqueous solution of Compound 2-1 were dissolved in 16.2 g of propylene glycol monomethyl ether (PGME). Next, 70% nitric acid aqueous solution 1
An aqueous solution in which 0.7 mg was dissolved in 764 mg of water was added dropwise, and the reaction solution was stirred at room temperature for 5 hours. Thereafter, stirring was stopped, and the solution was concentrated under reduced pressure to remove low-boiling substances and water, followed by further filtration. A coating solution was prepared by adding a solvent having the same mass as the filtrate.
Example 4
4 g of Compound 1-15 and 479 mg of a 2.4% aqueous solution of Compound 2-1 were dissolved in 19.4 g of propylene glycol monomethyl ether (PGME). Next, an aqueous solution in which 10.7 mg of 70% nitric acid aqueous solution was dissolved in 765 mg of water was dropped, and the reaction solution was stirred at room temperature for 5 hours. Thereafter, stirring was stopped, and the solution was concentrated under reduced pressure to remove low-boiling substances and water, followed by further filtration. A coating solution was prepared by adding a solvent having the same mass as the filtrate.
Example 5
4 g of Compound 1-21 and 477 mg of a 2.4% aqueous solution of Compound 2-1 were dissolved in 19.4 g of propylene glycol monomethyl ether (PGME). Next, an aqueous solution in which 10.6 mg of 70% nitric acid aqueous solution was dissolved in 761 mg of water was added dropwise, and the reaction solution was stirred at room temperature for 5 hours. Thereafter, stirring was stopped, and the solution was concentrated under reduced pressure to remove low-boiling substances and water, followed by further filtration. A coating solution was prepared by adding a solvent having the same mass as the filtrate.
[Examples 6 to 8]
In Example 4, instead of compound 2-1, compound 4-2, compound 2-17, compound 2-19 was used in the same manner as in Example 4 except that 478 mg of 2.4% aqueous solution was used. Coating solutions of Examples 6 to 8 were prepared.
[Comparative Example 1]
A coating solution was prepared in the same manner as in Example 5 except that Compound 2-1 was not used.
[Comparative Example 2]
2.5 g of 477 mg of a 2.4% aqueous solution of the following compound A and compound 2-1 was dissolved in 13.4 g of propylene glycol monomethyl ether (PGME). Next, an aqueous solution in which 10.6 mg of 70% nitric acid aqueous solution was dissolved in 763 mg of water was added dropwise, and the reaction solution was stirred at room temperature for 5 hours. Thereafter, stirring was stopped, and the solution was concentrated under reduced pressure to remove low-boiling substances and water, followed by further filtration. A coating solution was prepared by adding a solvent having the same mass as the filtrate.

[Preparation of insulating film]
The coating solution prepared as described above was spin-coated on a silicon substrate to a film thickness of 3500 A, and dried on a hot plate at 110 ° C. for 1 minute and 200 ° C. for 1 minute to remove the solvent. Next, the dried silicon substrate was transferred to a clean oven and heat-treated at 400 ° C. for 1 hour in nitrogen having an oxygen concentration of 10 ppm or less. The intended insulating film was obtained.
[Measurement of dielectric constant]
After leaving for 24 hours at a temperature of 24 ° C. and a humidity of 50%, the dielectric constant was measured at 1 MHz using a mercury probe manufactured by Four Dimensions and an HP4285A LCR meter manufactured by Hewlett-Packard. The measurement results are shown in Table 2.
[Measurement of elastic modulus (Young's modulus)]
The elastic modulus at 1/10 depth of the film thickness was measured using Nanoindenter SA2 (manufactured by MTS). The measurement results are shown in Table 2.

本発明の絶縁材料形成用組成物により調製した絶縁膜は誘電率が低く、強度も高く、優れた性能を有することがわかる。

It can be seen that the insulating film prepared by the composition for forming an insulating material of the present invention has a low dielectric constant, high strength, and excellent performance.

Claims (6)

A compound obtained by hydrolyzing and condensing at least one silane compound selected from the compound represented by the general formula (1), its hydrolysis and its condensate in the presence of a substituted or unsubstituted ammonium salt A method for producing a composition for forming an insulating material.

In General Formula (1), X ¹ represents a hydrolyzable group, R ¹ represents an alkyl group, an aryl group, or a heterocyclic group, n ₁ represents an integer of ₁ to 3, and m ₁ represents 2 or more. Represents an integer. L ¹ represents a single bond or a divalent linking group, and A represents a group containing a cage structure.   The production method according to claim 1, wherein in formula (1), A contains a diamantyl group. The production method according to claim 1 or 2, wherein the ammonium salt is represented by the following general formula (2).

In the general formula (2), R ^{2 to} R ⁵ each independently represents a hydrogen atom, an alkyl group, or an aryl group. n represents an integer of 1 to 3. X represents an n-valent anionic group. R ^{2 to} R ⁵ may be linked to each other to form a ring structure.   The composition for insulating material formation obtained by the method in any one of Claims 1-3.   An insulating material formed from the composition according to claim 4.   An insulating film formed from the composition according to claim 4.