JP2018172321A - Cyclic siloxane compound, production method thereof, method of producing electric insulating film using the same, and film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cyclic siloxane compound which has a high vapor pressure and an excellent vaporization property, exhibits a high deposition rate by the PECVD method, and is liquid at room temperature.SOLUTION: The cyclic siloxane compound is represented by general formula (1). (Rrepresents a C3-5 alkyl group; Rand Rmay each independently represent a C1-3 alkyl group, and may together form a C3-6 alkylene group; and n, m and o are each independently 1 or 2 and satisfy n+m+o=4.)SELECTED DRAWING: None

Description

  The present invention relates to a cyclic siloxane compound useful as a precursor for a film formation process by a plasma enhanced chemical vapor deposition (PECVD) method, and an electrical device for a semiconductor device which is manufactured by using the compound and has excellent insulation and mechanical strength. It relates to an insulating film.

  In a highly integrated multi-layer semiconductor integrated circuit, the minimum limit of the wiring interval of the circuit is determined by the relative dielectric constant of the insulating material, so that the interlayer insulating film is an important component. This is produced mainly by vapor deposition. In general, an interlayer insulating film is often manufactured by vaporizing a low molecular weight siloxane compound and introducing the siloxane compound into a film forming apparatus and using a plasma enhanced chemical vapor deposition (PECVD) method. By appropriately changing the organic group of the siloxane compound, it is possible to control the relative dielectric constant, film hardness, elastic modulus, film forming speed, and the like of the interlayer insulating film to be manufactured. Patent Document 1 discloses an interlayer insulating film manufactured using 2,4,6-triisopropyl-2,4,6-trivinylcyclotrisiloxane (compound A) as a precursor. However, the film forming speed of this is not always sufficient, and further improvement of the film forming speed is desired. Patent Document 2 discloses a method for producing an electrical insulating film produced by using a cyclic siloxane compound having a cyclic alkanediyl group and an alkenediyl group on silicon as a precursor. However, all of these precursors are crystalline solid substances, and have a problem in handling such as heating required for melting when the liquid is fed to the film forming apparatus.

JP 2007-96237 A US Pat. No. 6,572,923

  High vapor pressure, excellent vaporization characteristics, high film formation rate by PECVD method, manufacturing liquid cyclic siloxane compound at room temperature, and using this cyclic siloxane compound as a precursor, the mechanical strength obtained by subjecting to PECVD process It is an object of the present invention to provide an excellent electrical insulating film having a low dielectric constant and a semiconductor electronic device comprising the same.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a novel cyclic siloxane compound having at least one vinyl group on a silicon atom has a performance capable of solving the above-mentioned problems. It came to complete.

That is, this invention consists of the following structures.
(1)
General formula (1)

(In the formula, R ¹ represents an alkyl group having 3 to 5 carbon atoms. R ² and R ³ each independently represent an alkyl group having 1 to 3 carbon atoms. R ² and R ³ are combined together. A cyclic siloxane compound represented by the following formula: n, m and o are each independently 1 or 2, and n + m + o = 4 may be formed.
(2)
The cyclic siloxane compound according to (1), wherein R ¹ is an isopropyl group, and R ² and R ³ are a butane-1,4-diyl group.
(3)
The cyclic siloxane compound according to (1) or (2), wherein m and n are 1 and o is 2.
(4)
The cyclic siloxane compound according to (1) or (2), wherein m and o are 1 and n is 2.
(5)
The cyclic siloxane compound according to (1) or (2), wherein n and o are 1 and m is 2.
(6)
General formula (2)

(Wherein R ¹ represents an alkyl group having 3 to 5 carbon atoms) and a general formula (3)

(In the formula, R ² and R ³ each independently represents an alkyl group having 1 to 3 carbon atoms. R ² and R ³ may together form an alkylene group having 3 to 6 carbon atoms. X ¹ represents a halogen atom.) The method for producing a cyclic siloxane compound according to (1), (2) or (3), wherein the dihalosilane represented by (1) is reacted.
(7)
General formula (4)

(Wherein R ¹ represents an alkyl group having 3 to 5 carbon atoms, X ² represents a halogen atom), and a general formula (5)

(In the formula, R ² and R ³ each independently represents an alkyl group having 1 to 3 carbon atoms. R ² and R ³ may together form an alkylene group having 3 to 6 carbon atoms. The method for producing a cyclic siloxane compound according to (1), (2) or (3), wherein the dialkylsilane represented by formula (1) is reacted.
(8)
General formula (4)

(Wherein R ¹ represents an alkyl group having 3 to 5 carbon atoms, X ² represents a halogen atom), and a general formula (6)

(In the formula, R ² and R ³ each independently represents an alkyl group having 1 to 3 carbon atoms. R ² and R ³ may together form an alkylene group having 3 to 6 carbon atoms. .) The method for producing a cyclic siloxane compound according to (1), (2) or (5), wherein the dihydroxydisiloxane represented by formula (1) is reacted.
(9)
General formula (7) in the presence of Lewis acid

(Wherein R ¹ represents an alkyl group having 3 to 5 carbon atoms. Two R ^{4 s} are the same or different and are a hydrogen atom or a methyl group) and a general formula (8)

(In the formula, R ² and R ³ each independently represents an alkyl group having 1 to 3 carbon atoms. R ² and R ³ may together form an alkylene group having 3 to 6 carbon atoms. The method for producing a cyclic siloxane compound according to (1), (2) or (5), wherein the dihydrodisiloxane represented by the formula (1) is reacted.
(10)
General formula (5)

(In the formula, R ² and R ³ each independently represents an alkyl group having 1 to 3 carbon atoms. R ² and R ³ may together form an alkylene group having 3 to 6 carbon atoms. )) And a general formula (9)

(Wherein R ¹ represents an alkyl group having 3 to 5 carbon atoms, X ³ represents a halogen atom), (1), (2 ) Or the method for producing a cyclic siloxane compound according to (4).
(11)
A method for producing an electrical insulating film, comprising using the cyclic siloxane compound according to any one of (1) to (5) as a precursor of a plasma enhanced chemical vapor deposition method.
(12)
An electrical insulating film produced by using the cyclic siloxane compound according to any one of (1) to (5) as a precursor of a plasma enhanced chemical vapor deposition method.
(13)
A semiconductor electronic device using the electrical insulating film according to (12).

  All of the cyclic siloxane compounds of the present invention are low-viscosity and easy-to-handle liquid substances at room temperature, and heating is not required when the liquid is fed to a film forming apparatus. In addition, by using the cyclic siloxane of the present invention as a precursor in a PECVD process, a low dielectric constant insulating film having excellent mechanical strength can be produced at a high film formation rate, and it can be suitably used for semiconductor electronic devices.

Hereinafter, the present invention will be specifically described. First, definitions of R ¹ , R ² and R ³ in the general formulas (1) to (9) will be described. R ¹ is an alkyl group having 3 to 5 carbon atoms, and may be linear, branched or cyclic. Specifically, propyl group, isopropyl group, cyclopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclopentyl group, pentyl group, sec-pentyl group, isopentyl group, and cyclopentyl group can be exemplified. . R ² and R ³ are each independently an alkyl group having 1 to 3 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a cyclopropyl group. R ² and R ³ may together form an alkanediyl group having 3 to 6 carbon atoms. Examples of such alkanediyl groups include propane-1,3-diyl group, butane-1,4-diyl group, butane-1,3-diyl group, pentane-1,3-diyl group, and pentane-1,4. -Diyl group, pentane-1,5-diyl group, pentane-2,4-diyl group, hexane-1,3-diyl group, hexane-1,4-diyl group, hexane-1,5-diyl group, hexane A -1,6-diyl group can be exemplified. In the cyclic siloxane compound of the present invention, R ¹ is preferably a propyl group or an isopropyl group, and more preferably an isopropyl group, from the viewpoint of providing a film having good performance in PECVD film formation. R ² and R ³ are each preferably a methyl group, an ethyl group or a propyl group. R ² and R ³ together are a propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, and hexane-1,6-diyl group. The butane-1,4-diyl group or the pentane-1,5-diyl group is more preferable.

  n, m and o are each independently 1 or 2, and satisfy n + m + o = 4, and among them, (m, n, o) is (1, 1, 2), (1, 2, 1) or (2 1, 1) is preferred.

  Next, the manufacturing method of the cyclic siloxane compound shown by General formula (1) is demonstrated. In the method of the present invention, among the cyclic siloxane compounds represented by the general formula (1), those in which m and n are 1 and o is 2,

(Wherein R ¹ represents a group represented by the above general formula (1)), and the dihydroxysilane (2) represented by the general formula (3)

(In the formula, R ² and R ³ represent a group represented by the above general formula (1). X ¹ represents a halogen atom). Method 1).

  The dihydroxysilane represented by the general formula (2) can be obtained by synthesizing by using production methods reported in many non-patent documents. Those skilled in the art can prepare dihydroxysilane (2) by hydrolysis reaction of vinylalkyldihalosilane, hydrolysis reaction of vinylalkyldialkoxysilane, hydrolysis reaction using a catalyst of vinylalkyldihydrosilane, and the like. Can be easily manufactured.

Further, the X ¹ dihalosilane represented by the general formula (3) a halogen atom, fluorine, chlorine, bromine or iodine. As the halogen atom, chlorine or bromine is preferable, and chlorine is more preferable. Among dihalosilanes (3), dichlorodimethylsilane, dichlorodiethylsilane, 1,1-dichloro-1-silacyclobutane and the like can be carried out using commercially available products. Moreover, it can implement by using the dihalosilane (3) synthesize | combined according to the method reported in the nonpatent literature. Dihalosilane (3) can be produced by a person skilled in the art by direct reaction of metal silicon with organic halide, reaction of silicon tetrachloride with organic alkylmagnesium halide, reaction of silicon tetrachloride with organolithium reagent, etc. If there is, it can be manufactured easily.

  Production method 1 is desirably carried out in the presence of an organic amine because the coexistence of the organic amine significantly increases the reaction rate. As the organic amine, a known organic amine such as triethylamine, diethylamine, tripropylamine, aniline, pyridine or quinoline can be appropriately selected and used. It is preferable to carry out in the presence of triethylamine or pyridine from the viewpoint of good yield and easy purification. The amount of the organic amine used is selected from a range of 2 to 2000 times mol, preferably 2 to 200 times mol, more preferably 2 to 10 times mol, per mol of the dihalosilane compound (3).

  The production atmosphere is not particularly limited, but is preferably carried out in an inert atmosphere using nitrogen, helium or argon in terms of a good yield.

  The reaction temperature is not particularly limited, and those skilled in the art can use general temperature conditions for producing a cyclic siloxane compound. As a specific example, the cyclic siloxane compound of the present invention can be obtained with good yield at a reaction temperature appropriately selected from a temperature range of −100 ° C. to 200 ° C. From the viewpoint of yield, safety, and operability, an operating temperature selected from the range of -80 to 50 ° C is preferable. The reaction time is appropriately determined, but it is preferable to carry out the reaction with a reaction time appropriately selected from the range of 1 minute to 200 hours.

It is preferable to implement the manufacturing method 1 in an organic solvent at a point with a sufficient yield. The usable organic solvent is not limited as long as it does not inhibit the reaction. Specifically, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, and fats such as cyclopentane, pentane, hexane, cyclohexane, and heptane. Aromatic hydrocarbons, diethyl ether, diisopropyl ether, cyclopentyl methyl ether (CPME), tetrahydrofuran (THF), ethers such as 1,4-dioxane, 1,2-dimethoxyethane, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone Can be illustrated. These organic solvents can be used singly or as a mixture of plural kinds at an arbitrary ratio. In terms of good yield and short reaction time, the organic solvent is preferably an ether, preferably diethyl ether or THF, and more preferably THF. Moreover, if an organic amine is used in excess, an organic solvent may not be used.
In addition, among the cyclic siloxane compounds represented by the general formula (1), those in which m and n are 1 and o is 2 should be manufactured by manufacturing method 2 which is a method different from the method of manufacturing method 1. Can do. That is, the production method 2 is a general formula (4).

(In the formula, ^{R 1} .X ² shows the same group as ^{R 1} in formula (1) is a halogen atom.) And vinylsilane (4) represented by the general formula (5)

(Wherein, R ² and R ³ represents the same group as R ² and R ³ in the general formula (1).) Is a manufacturing method by reacting a dialkyl silane (5) represented by.

X ² of the vinylsilane represented by the general formula (4) is a halogen atom, and is fluorine, chlorine, bromine or iodine. As the halogen atom, chlorine or bromine is preferable, and chlorine is more preferable. Vinylsilane (4) can be synthesized and carried out according to the method reported in non-patent literature. As a method for producing vinyl silane (4), those skilled in the art can use chlorination reaction of alkyl dialkoxy vinyl silane with acyl halide, reaction of trichlorovinyl silane with organic alkyl magnesium halide, reaction of alkyl trichloro silane with vinyl magnesium halide, etc. If there is, it can be manufactured easily. Moreover, the manufacturing method currently reported by many nonpatent literature can be applied and manufactured for manufacture of the dialkylsilane shown by General formula (5). As these production methods, those skilled in the art can easily produce dialkyldihalosilane hydrolysis reaction, dialkyldialkoxysilane hydrolysis reaction, dialkyldihydrosilane catalyst hydrolysis reaction, etc. I can do it.

  Production method 2 is desirably carried out in the presence of an organic amine because the coexistence of the organic amine significantly increases the reaction rate. As the organic amine, a known organic amine such as triethylamine, diethylamine, tripropylamine, aniline, pyridine or quinoline can be appropriately selected and used. It is preferable to carry out in the presence of triethylamine or pyridine from the viewpoint of yield and easy purification. The amount of the organic amine used is selected from the range of 2 to 2000 times mol, preferably 2 to 200 times mol, more preferably 2 to 10 times mol, per mol of vinylsilane (4).

  The production atmosphere is not particularly limited, but it is preferably carried out in an inert atmosphere using nitrogen, helium or argon from the viewpoint of good yield.

  The reaction temperature is not particularly limited, and those skilled in the art can use general temperature conditions for producing a cyclic siloxane compound. As a specific example, the cyclic siloxane compound (1) of the present invention can be obtained with good yield at a reaction temperature appropriately selected from a temperature range of −100 ° C. to 200 ° C. From the viewpoint of yield, safety, and operability, an operating temperature selected from the range of -80 to 50 ° C is preferable. The reaction time is appropriately determined, but it is preferable to carry out the reaction with a reaction time appropriately selected from the range of 1 minute to 200 hours.

  This production method is preferably carried out in an organic solvent in terms of a good yield. The usable organic solvent is not limited as long as it does not inhibit the reaction. Specifically, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, and fats such as cyclopentane, pentane, hexane, cyclohexane, and heptane. Aromatic hydrocarbons, diethyl ether, diisopropyl ether, cyclopentyl methyl ether (CPME), tetrahydrofuran (THF), ethers such as 1,4-dioxane, 1,2-dimethoxyethane, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone Can be illustrated. These organic solvents can be used singly or as a mixture of plural kinds at an arbitrary ratio. In terms of good yield and short reaction time, the organic solvent is preferably an ether, diethyl ether and THF are preferred, and THF is more preferred. Moreover, if an organic amine is used in excess, an organic solvent may not be used.

  Specific examples of cyclic siloxane compounds in which m and n are 1 and o is 2 among the cyclic siloxane compounds of the present invention include 4,4,8,8-di (propane-1,3-diyl) -2. , 6-dipropyl-2,6-divinylcyclotetrasiloxane, 4,4,8,8-di (propane-1,3-diyl) -2,6-diisopropyl-2,6-divinylcyclotetrasiloxane, 4, 4,8,8-di (propane-1,3-diyl) -2,6-dicyclopropyl-2,6-divinylcyclotetrasiloxane, 4,4,8,8-di (butane-1,4- Diyl) -2,6-dipropyl-2,6-divinylcyclotetrasiloxane, 4,4,8,8-di (butane-1,4-diyl) -2,6-diisopropyl-2,6-divinylcyclotetra Siloxane, 4, 4, 8, 8 Di (butane-1,4-diyl) -2,6-dicyclopropyl-2,6-divinylcyclotetrasiloxane, 4,4,8,8-di (butane-1,3-diyl) -2,6 -Dipropyl-2,6-divinylcyclotetrasiloxane, 4,4,8,8-di (butane-1,3-diyl) -2,6-diisopropyl-2,6-divinylcyclotetrasiloxane, 4,4, 8,8-di (butane-1,3-diyl) -2,6-dicyclopropyl-2,6-divinylcyclotetrasiloxane, 4,4,8,8-di (pentane-1,4-diyl) -2,6-dipropyl-2,6-divinylcyclotetrasiloxane, 4,4,8,8-di (pentane-1,4-diyl) -2,6-diisopropyl-2,6-divinylcyclotetrasiloxane, 4,4,8,8-di ( Nthane-1,4-diyl) -2,6-dicyclopropyl-2,6-divinylcyclotetrasiloxane, 4,4,8,8-di (pentane-1,3-diyl) -2,6-dipropyl -2,6-divinylcyclotetrasiloxane, 4,4,8,8-di (pentane-1,3-diyl) -2,6-diisopropyl-2,6-divinylcyclotetrasiloxane, 4,4,8, 8-di (pentane-1,3-diyl) -2,6-dicyclopropyl-2,6-divinylcyclotetrasiloxane, 4,4,8,8-di (pentane-2,4-diyl) -2 , 6-dipropyl-2,6-divinylcyclotetrasiloxane, 4,4,8,8-di (pentane-2,4-diyl) -2,6-diisopropyl-2,6-divinylcyclotetrasiloxane, 4, 4,8,8-di ( Pentane-2,4-diyl) -2,6-dicyclopropyl-2,6-divinylcyclotetrasiloxane, 4,4,8,8-di (pentane-1,5-diyl) -2,6-dipropyl -2,6-divinylcyclotetrasiloxane, 4,4,8,8-di (pentane-1,5-diyl) -2,6-diisopropyl-2,6-divinylcyclotetrasiloxane, 4,4,8, 8-di (pentane-1,5-diyl) -2,6-dicyclopropyl-2,6-divinylcyclotetrasiloxane, 4,4,8,8-di (hexane-1,6-diyl) -2 , 6-dipropyl-2,6-divinylcyclotetrasiloxane, 4,4,8,8-di (hexane-1,6-diyl) -2,6-diisopropyl-2,6-divinylcyclotetrasiloxane, 4, 4,8,8-di Hexane-1,6-diyl) -2,6-cyclopropyl-2,6-divinyl cyclotetrasiloxane a can be exemplified. 4,4,8,8-di (butane-1,4-diyl) -2,6-diisopropyl-2,6-divinylcyclotetrasiloxane in that the film formation rate is low and the film has a low relative dielectric constant. 4,4,8,8-di (pentane-1,5-diyl) -2,6-diisopropyl-2,6-divinylcyclotetrasiloxane, 4,4,8,8-di (butane-1,4) -Diyl) -2,6-dipropyl-2,6-divinylcyclotetrasiloxane, 4,4,8,8-di (pentane-1,5-diyl) -2,6-dipropyl-2,6-divinylcyclo Tetrasiloxane is preferred, and 4,4,8,8-di (butane-1,4-diyl) -2,6-diisopropyl-2,6-divinylcyclotetrasiloxane is particularly preferred.

  Next, production method 3 of the cyclic siloxane compound (1) in which n and o are 1 and m is 2 will be described. In the production method 3, the general formula (4)

(Wherein R ¹ is the same as R ¹ in the above general formula (1). X ² represents a halogen atom) and the general formula (6).

(Wherein R ² and R ³ are the same as R ² and R ³ in the general formula (1)).

  The vinyl silane represented by the general formula (4) has the same meaning as the vinyl silane represented by the general formula (4) in the production method 2.

  In the production method 3, since the coexistence of the organic amine remarkably increases the reaction rate, it is desirable to carry out in the presence of the organic amine. As the organic amine, a known organic amine such as triethylamine, diethylamine, tripropylamine, aniline, pyridine or quinoline can be appropriately selected and used. It is preferable to carry out in the presence of triethylamine or pyridine from the viewpoint of yield and easy purification. The amount of the organic amine used is selected from the range of 2 to 2000 times mol, preferably 2 to 200 times mol, more preferably 2 to 10 times mol, per mol of vinylsilane (4).

  The production atmosphere is not particularly limited, but is preferably carried out in an inert atmosphere using nitrogen, helium or argon in terms of a good yield.

  The reaction temperature is not particularly limited, and those skilled in the art can use general temperature conditions for producing a cyclic siloxane compound. As a specific example, the cyclic siloxane compound of the present invention can be obtained with good yield at a reaction temperature appropriately selected from a temperature range of −100 ° C. to 200 ° C. From the viewpoint of yield, safety, and operability, an operating temperature selected from the range of -80 to 50 ° C is preferable. The reaction time is appropriately determined, but it is preferable to carry out the reaction with a reaction time appropriately selected from the range of 1 minute to 200 hours.

  It is preferable to implement the manufacturing method 3 in an organic solvent at a point with a sufficient yield. The usable organic solvent is not limited as long as it does not inhibit the reaction. Specifically, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, and fats such as cyclopentane, pentane, hexane, cyclohexane, and heptane. Aromatic hydrocarbons, diethyl ether, diisopropyl ether, cyclopentyl methyl ether (CPME), tetrahydrofuran (THF), ethers such as 1,4-dioxane, 1,2-dimethoxyethane, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone Can be illustrated. These organic solvents can be used singly or as a mixture of plural kinds at an arbitrary ratio. In terms of good yield and short reaction time, the organic solvent is preferably an ether, more preferably diethyl ether and THF, and most preferably THF. Moreover, if an organic amine is used in excess, an organic solvent may not be used.

  Further, among the cyclic siloxane compounds represented by the general formula (1), those in which n and o are 1 and m is 2 can be produced by the following production method 4 in addition to the production method 3. That is, in the production method 4, in the presence of a Lewis acid catalyst, the general formula (7)

(Wherein R ¹ is the same as R ¹ in the above general formula (1). R ⁴ is a hydrogen atom or a methyl group) and the general formula (8)

(Wherein R ² and R ³ are the same as R ² and R ³ in the general formula (1)).

  The dialkoxysilane represented by the general formula (7) can be produced by applying methods reported in many non-patent documents. The dialkoxysilane (7) can be produced by a methoxylation reaction of vinylalkyldihalosilane with methanol, a methoxylation reaction of vinylalkyldihalosilane with metal methoxide, vinyltrimethoxysilane and an alkylmagnesium halide reagent or alkyllithium. Those skilled in the art can easily produce the reaction by reaction of alkyltrimethoxysilane with vinylmagnesium halide or vinyllithium.

  The production of dihydrodisiloxane represented by the general formula (8) can be carried out by applying methods reported in many non-patent documents. As a method for producing the dihydrodisiloxane compound, those skilled in the art can easily produce the dihydrohalosiloxane by synthesis by hydrolysis of dialkylhalohydrosilane, reduction reaction by metal hydride of dialkyldichlorodisiloxane, or the like.

  It is essential to carry out the production of the cyclic siloxane compound (1) by the production method 4 in the presence of a Lewis acid catalyst. As the Lewis acid catalyst, inorganic indium salts such as indium chloride, indium bromide or indium iodide, gallium salts such as gallium chloride or gallium bromide, and organic boron compounds such as tris (pentafluorophenyl) boron are used. I can do it. From the viewpoint of high yield and short production time, it is preferable to use an organic boron compound as a catalyst, and tris (pentafluorophenyl) boron is more preferable. The amount of the Lewis acid catalyst used is selected from the range of 0.0001 to 1000 equivalents, preferably 0.001 to 1 equivalent, more preferably 0.01-0 with respect to 1 molar equivalent of dialkoxysilane (7). .1 equivalent. The production atmosphere is not particularly limited, but is preferably carried out in an inert atmosphere using nitrogen, helium or argon in terms of high yield.

  The reaction temperature is not particularly limited, and those skilled in the art can use general temperature conditions for producing a cyclic siloxane compound. As a specific example, the cyclic siloxane compound of the present invention can be obtained with good yield at a reaction temperature appropriately selected from a temperature range of −100 ° C. to 200 ° C. From the viewpoint of yield, safety, and operability, an operating temperature selected from the range of -80 to 100 ° C is preferable. The reaction time is appropriately determined, but it is preferable to carry out the reaction with a reaction time appropriately selected from the range of 1 minute to 200 hours.

  This production method is preferably carried out in an organic solvent in terms of a good yield. The usable organic solvent is not limited as long as it does not inhibit the reaction. Specifically, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, and aliphatic hydrocarbons such as hexane, heptane, octane, and decalin. And ethers such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether (CPME), tetrahydrofuran (THF), 1,4-dioxane, 1,2-dimethoxyethane, and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone I can do it. These organic solvents can be used singly or as a mixture of plural kinds at an arbitrary ratio. In terms of good yield and short reaction time, the organic solvent is preferably an aromatic hydrocarbon such as benzene or toluene, more preferably toluene.

  Specific examples of cyclic siloxane compounds of the present invention in which n and o are 1 and m is 2 are 2-propyl-2-vinyl-4,4,6,6-tetramethylcyclohexane. Trisiloxane, 2-isopropyl-2-vinyl-4,4,6,6-tetramethylcyclotrisiloxane, 2-cyclopropyl-2-vinyl-4,4,6,6-tetramethylcyclotrisiloxane, 2- Propyl-2-vinyl-4,4,6,6-tetraethylcyclotrisiloxane, 2-isopropyl-2-vinyl-4,4,6,6-tetraethylcyclotrisiloxane, 2-cyclopropyl-2-vinyl-4 , 4,6,6-tetraethylcyclotrisiloxane, 2-propyl-2-vinyl-4,6-dimethyl-4,6-diethylcyclotrisiloxane, Isopropyl-2-vinyl-4,6-dimethyl-4,6-diethylcyclotrisiloxane, 2-cyclopropyl-2-vinyl-4,6-dimethyl-4,6-diethylcyclotrisiloxane, 2-propyl-2 -Vinyl-4,4,6,6-di (propane-1,3-diyl) cyclotrisiloxane, 2-isopropyl-2-vinyl-4,4,6,6-di (propane-1,3-diyl) ) Cyclotrisiloxane, 2-cyclopropyl-2-vinyl-4,4,6,6-di (propane-1,3-diyl) cyclotrisiloxane, 2-propyl-2-vinyl-4,4,6, 6-di (butane-1,4-diyl) cyclotrisiloxane, 2-isopropyl-2-vinyl-4,4,6,6-di (butane-1,4-diyl) cyclotrisiloxane, 2-cyclopro Ru-2-vinyl-4,4,6,6-di (butane-1,4-diyl) cyclotrisiloxane, 2-propyl-2-vinyl-4,4,6,6-di (butane-1, 3-diyl) cyclotrisiloxane, 2-isopropyl-2-vinyl-4,4,6,6-di (butane-1,3-diyl) cyclotrisiloxane, 2-cyclopropyl-2-vinyl-4,4 , 6,6-di (butane-1,3-diyl) cyclotrisiloxane, 2-propyl-2-vinyl-4,4,6,6-di (pentane-1,4-diyl) cyclotrisiloxane, 2, -Isopropyl-2-vinyl-4,4,6,6-di (pentane-1,4-diyl) cyclotrisiloxane, 2-cyclopropyl-2-vinyl-4,4,6,6-di (pentane- 1,4-diyl) cyclotrisiloxane, 2-propyl Lopyl-2-vinyl-4,4,6,6-di (pentane-1,3-diyl) cyclotrisiloxane, 2-isopropyl-2-vinyl-4,4,6,6-di (pentane-1, 3-diyl) cyclotrisiloxane, 2-cyclopropyl-2-vinyl-4,4,6,6-di (pentane-1,3-diyl) cyclotrisiloxane, 2-propyl-2-vinyl-4,4 , 6,6-di (pentane-2,4-diyl) cyclotrisiloxane, 2-isopropyl-2-vinyl-4,4,6,6-di (pentane-2,4-diyl) cyclotrisiloxane, 2, -Cyclopropyl-2-vinyl-4,4,6,6-di (pentane-2,4-diyl) cyclotrisiloxane, 2-propyl-2-vinyl-4,4,6,6-di (pentane- 1,5-diyl) cyclotrisiloxy 2-isopropyl-2-vinyl-4,4,6,6-di (pentane-1,5-diyl) cyclotrisiloxane, 2-cyclopropyl-2-vinyl-4,4,6,6-di (Pentane-1,5-diyl) cyclotrisiloxane, 2-propyl-2-vinyl-4,4,6,6-di (hexane-1,6-diyl) cyclotrisiloxane, 2-isopropyl-2-vinyl -4,4,6,6-di (hexane-1,6-diyl) cyclotrisiloxane, 2-cyclopropyl-2-vinyl-4,4,6,6-di (hexane-1,6-diyl) An example is cyclotrisiloxane. 2-propyl-2-vinyl-4,4,6,6-di (butane-1,4-diyl) cyclotrisiloxane, 2-isopropyl-2-vinyl- from the viewpoint of good film forming speed and vapor pressure 4,4,6,6-di (butane-1,4-diyl) cyclotrisiloxane, 2-propyl-2-vinyl-4,4,6,6-di (pentane-1,5-diyl) cyclotri Siloxane and 2-isopropyl-2-vinyl-4,4,6,6-di (pentane-1,5-diyl) cyclotrisiloxane are preferred, and 2-isopropyl-2-vinyl-4,4,6,6- Di (butane-1,4-diyl) cyclotrisiloxane is particularly preferred.

  Next, production of the cyclic siloxane compound represented by the general formula (1) where m and o are 1 and n is 2 (Production Method 5) will be described. In the production method 5, the general formula (5)

(Wherein, ^{R 2} and ^{R 3} are the same as ^{R 2} and ^{R 3} in the above general formula (1).) With a dialkyl silane represented by the general formula (9)

(Wherein R ¹ represents an alkyl group having 3 to 5 carbon atoms; X ³ represents a halogen atom).

For the production of the dialkylsilane represented by the general formula (5), production methods reported in many non-patent documents can be applied and used. As these production methods, those skilled in the art can easily produce dialkyldihalosilane hydrolysis reaction, dialkyldialkoxysilane hydrolysis reaction, dialkyldihydrosilane catalyst hydrolysis reaction, etc. I can do it. Moreover, the manufacturing method currently reported by many nonpatent literature can be used for the divinyl disiloxane shown by General formula (9). Those skilled in the art can easily prepare these by partial hydrolysis of alkylvinyldihalosilane, chlorination reaction of 1,3-dihydro-1,3-dialkyl-1,3-divinyldisiloxane, and the like. Can be manufactured. X ^{3 in the} divinyldisiloxane represented by the general formula (9) is a halogen atom, and is fluorine, chlorine, bromine or iodine. As the halogen atom, chlorine or bromine is preferable, and chlorine is more preferable.

  The production method 5 is desirably carried out in the presence of an organic amine because the coexistence of the organic amine significantly increases the reaction rate. As the organic amine, a known organic amine such as triethylamine, diethylamine, tripropylamine, aniline, pyridine or quinoline can be appropriately selected and used. It is preferable to carry out in the presence of triethylamine or pyridine from the viewpoint of yield and easy purification. The amount of the organic amine used is selected from a range of 2 to 2000 times mol, preferably 2 to 200 times mol, more preferably 2 to 10 times mol, per mol of dihalosilane (3).

  The production atmosphere is not particularly limited, but is preferably carried out in an inert atmosphere using nitrogen, helium or argon from the viewpoint of good yield.

  The reaction temperature is not particularly limited, and those skilled in the art can use general temperature conditions for producing a cyclic siloxane compound. As a specific example, the cyclic siloxane compound of the present invention can be obtained with good yield at a reaction temperature appropriately selected from a temperature range of −100 ° C. to 200 ° C. From the viewpoint of yield, safety, and operability, an operating temperature selected from the range of -80 to 50 ° C is preferable. The reaction time is appropriately determined, but it is preferable to carry out the reaction with a reaction time appropriately selected from the range of 1 minute to 200 hours.

  This production method is preferably carried out in an organic solvent in terms of a good yield. The usable organic solvent is not limited as long as it does not inhibit the reaction. Specifically, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, and fats such as cyclopentane, pentane, hexane, cyclohexane, and heptane. Aromatic hydrocarbons, diethyl ether, diisopropyl ether, cyclopentyl methyl ether (CPME), tetrahydrofuran (THF), ethers such as 1,4-dioxane, 1,2-dimethoxyethane, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone Can be illustrated. These organic solvents can be used singly or as a mixture of plural kinds at an arbitrary ratio. In terms of good yield and short reaction time, the organic solvent is preferably an ether, more preferably diethyl ether and THF, and most preferably THF. Moreover, if an organic amine is used in excess, an organic solvent may not be used.

  Specific examples of the cyclic siloxane compound that can be produced by the production method 5 include 2,4-dipropyl-2,4-divinyl-6,6-dimethylcyclotrisiloxane, 2,4-diisopropyl-2,4-divinyl. -6,6-dimethylcyclotrisiloxane, 2,4-dicyclopropyl-2,4-divinyl-6,6-dimethylcyclotrisiloxane, 2,4-dipropyl-2,4-divinyl-6,6-diethyl Cyclotrisiloxane, 2,4-diisopropyl-2,4-divinyl-6,6-diethylcyclotrisiloxane, 2,4-dicyclopropyl-2,4-divinyl-6,6-diethylcyclotrisiloxane, 2, 4-dipropyl-2,4-divinyl-6-methyl-6-ethylcyclotrisiloxane, 2,4-diisopropyl-2,4-divini -6-methyl-6-ethylcyclotrisiloxane, 2,4-dicyclopropyl-2,4-divinyl-6-methyl-6-ethylcyclotrisiloxane, 2,4-dipropyl-2,4-divinyl-6 , 6- (propane-1,3-diyl) cyclotrisiloxane, 2,4-diisopropyl-2,4-divinyl-6,6- (propane-1,3-diyl) cyclotrisiloxane, 2,4-di Cyclopropyl-2,4-divinyl-6,6- (propane-1,3-diyl) cyclotrisiloxane, 2,4-dipropyl-2,4-divinyl-6,6- (butane-1,3-diyl) ) Cyclotrisiloxane, 2,4-diisopropyl-2,4-divinyl-6,6- (butane-1,3-diyl) cyclotrisiloxane, 2,4-dicyclopropyl-2,4-divini -6,6- (butane-1,3-diyl) cyclotrisiloxane, 2,4-dipropyl-2,4-divinyl-6,6- (butane-1,4-diyl) cyclotrisiloxane, 2,4 -Diisopropyl-2,4-divinyl-6,6- (butane-1,4-diyl) cyclotrisiloxane, 2,4-dicyclopropyl-2,4-divinyl-6,6- (butane-1,4) -Diyl) cyclotrisiloxane, 2,4-dipropyl-2,4-divinyl-6,6- (pentane-1,3-diyl) cyclotrisiloxane, 2,4-diisopropyl-2,4-divinyl-6 6- (pentane-1,3-diyl) cyclotrisiloxane, 2,4-dicyclopropyl-2,4-divinyl-6,6- (pentane-1,3-diyl) cyclotrisiloxane, 2,4- Dipropyl -2,4-divinyl-6,6- (pentane-1,4-diyl) cyclotrisiloxane, 2,4-diisopropyl-2,4-divinyl-6,6- (pentane-1,4-diyl) cyclo Trisiloxane, 2,4-dicyclopropyl-2,4-divinyl-6,6- (pentane-1,4-diyl) cyclotrisiloxane, 2,4-dipropyl-2,4-divinyl-6,6- (Pentane-1,5-diyl) cyclotrisiloxane, 2,4-diisopropyl-2,4-divinyl-6,6- (pentane-1,5-diyl) cyclotrisiloxane, 2,4-dicyclopropyl- 2,4-divinyl-6,6- (pentane-1,5-diyl) cyclotrisiloxane, 2,4-dipropyl-2,4-divinyl-6,6- (pentane-2,4-diyl) cyclotrisilo Sun, 2,4-diisopropyl-2,4-divinyl-6,6- (pentane-2,4-diyl) cyclotrisiloxane, 2,4-dicyclopropyl-2,4-divinyl-6,6- ( Pentane-2,4-diyl) cyclotrisiloxane, 2,4-dipropyl-2,4-divinyl-6,6- (hexane-1,6-diyl) cyclotrisiloxane, 2,4-diisopropyl-2,4 -Divinyl-6,6- (hexane-1,6-diyl) cyclotrisiloxane, 2,4-dicyclopropyl-2,4-divinyl-6,6- (hexane-1,6-diyl) cyclotrisiloxane Can be illustrated. 2,4-diisopropyl-2,4-divinyl-6,6-dimethylcyclotrisiloxane, 2,4-diisopropyl-2,4-divinyl-6,6-diethyl from the viewpoint of good film forming speed and vapor pressure Cyclotrisiloxane, 2,4-diisopropyl-2,4-divinyl-6,6- (butane-1,4-diyl) cyclotrisiloxane, 2,4-diisopropyl-2,4-divinyl-6,6- ( Pentane-1,4-diyl) cyclotrisiloxane is preferred, and 2,4-diisopropyl-2,4-divinyl-6,6- (butane-1,4-diyl) cyclotrisiloxane is particularly preferred.

  Next, a method for producing an electrical insulating film using the cyclic siloxane compound (1) of the present invention as a precursor of a plasma enhanced chemical vapor deposition method (PECVD method) will be described.

  The PECVD method vaporizes an insulating film material such as organosilane by a vaporizer, introduces it into a film forming chamber, applies it to an electrode in the film forming chamber with a high frequency power source, generates plasma, and forms a film forming chamber. An apparatus for forming a plasma polymerized film on an inner silicon substrate or the like. At this time, a gas such as argon or helium, or an oxidant such as oxygen or nitrous oxide may be introduced for the purpose of generating plasma. When a film is formed using the cycloaliphatic siloxane compound (1) of the present invention by a PECVD apparatus, a thin film suitable as a low dielectric constant material (low-k material) for semiconductor devices can be formed.

  Although the film-forming method using the cyclic siloxane compound (1) of the present invention is not limited, it is preferable to form the insulating film under PECVD conditions that leave the cyclic siloxane structure of the cyclic siloxane compound (1). An insulating film containing a cyclic siloxane structure is a porous insulating film having a pore diameter of 1 nm or less of an organic cyclic siloxane compound as a main pore diameter, has low dielectric constant characteristics, and has high mechanical properties and high heat conductivity. It is a thin film that is particularly suitable as a low dielectric constant material (low-k material) for semiconductor devices. As PECVD conditions at this time, for example, it is preferable to perform PECVD film formation with a relatively low plasma power (W: voltage × current) so as not to destroy the cyclic siloxane structure. Specifically, it is preferably performed in the range of 1.0 W to 2000 W, preferably 1.0 W to 1000 W. In particular, at this time, by using an organic cyclic siloxane in which a vinyl group and an isopropyl group are bonded to the same silicon atom, an insulating film having a lower dielectric constant characteristic can be formed at a high speed.

  Low dielectric constant made porous by heat-treating these materials at a temperature higher than the temperature at which any of secondary carbon atoms, alkenyl groups, and aryl groups and silicon atoms are cut, that is, 350 ° C. or higher, after film formation by CVD An insulating material can also be obtained. A preferable heat treatment temperature is 350 ° C. or higher at which the porosity is completed and 500 ° C. or lower at which the semiconductor device is not deteriorated.

  The electrical insulating film produced by using the cyclic siloxane compound (1) of the present invention as a precursor for plasma enhanced chemical vapor deposition (PECVD) is suitable for ULSI production using multilayer wiring, A semiconductor device using this is also included in the category of the present invention.

It is the schematic of the PECVD apparatus used in Examples 10-24 and Comparative Examples 1 and 2.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, this invention is not restrict | limited to these at all.
(Reference Example 1)

A 300 mL three-necked flask equipped with a stirrer, a dropping funnel and a Dimroth condenser was replaced with argon, and 12.4 g (91.0 mmol) of zinc chloride and 200 g (2.55 mol) of acetyl chloride were placed in the flask. From the dropping funnel, 82.9 g (51.7 mmol) of dimethoxyisopropylvinylsilane was added dropwise over 1 hour. The reaction mixture was stirred at 25 ° C. for 1 hour, and low boiling components were distilled off under reduced pressure. This was distilled at normal pressure (boiling point 140 ° C.) to obtain 73.2 g (yield: 83.7%, GC purity: 99%) of dichloroisopropylvinylsilane (Compound B) as a colorless liquid.
EI-MS (70 eV) m / z (relative intensity,%): 168 (M ⁺ , 2), 140 (15), 125 ([M- ⁱ Pr] ⁺ , 100), 113 (14), 101 (15 ); ¹ H-NMR (400 MHz, CDCl ₃ ): δ 1.12 (d, 6H, J = 7.2 Hz), 1.29 to 1.36 (m, 1H), 6.158 (d, 1H, J) = 8.0 Hz), 6.161 (d, 1 H, J = 9.6 Hz), 6.274 (dd, 1 H, J = 8.1, 9.5 Hz); ¹³ C-NMR (100 MHz, CDCl ₃ ) : Δ 15.9, 18.7, 130.7, 138.2; ²⁹ Si-NMR (79 MHz, CDCl ₃ ): δ-21.9; IR (neat, cm ⁻¹ ): 3070, 2954, 2935, 2871 , 1465, 1403, 995, 971, 881, 17,667.
(Reference Example 2)

In a 1 L three-necked flask equipped with a stirrer, a dropping funnel and a Dimroth condenser, 33.8 g (363 mmol) of aniline, 6.43 g (357 mmol) of distilled water, 600 mL of diethyl ether and 40 mL of acetone were placed. The container was cooled to 0 ° C., and 250 mL of dehydrated diethyl ether of 30.1 g (178 mmol) of dichloroisopropylvinylsilane (Compound B) was added dropwise from the dropping funnel over 1.5 hours. The reaction mixture was filtered, and the filtrate was concentrated and then dried under reduced pressure to obtain 17.8 g of isopropylvinylsilane-1,1-diol (compound C) as a white crystalline solid (yield: 75.9%, GC purity: 99%).
EI-MS (70 eV) m / z (relative intensity,%): 132 (M ⁺ , 32), 105 (22), 104 (100); ¹ H-NMR (400 MHz, (CD ₃ ) ₂ CO): δ0 _{.74~0.83 (m, 1H), 0.989} (CH 3, d, 6H, J = 7.3Hz), 5.035 (OH, s, 2H), 5.887 (dd, 1H, J = 5.8, 19.0 Hz), 5.961 (dd, 1 H, J = 5.8, 15.0 Hz), 6.045 (dd, 1 H, J = 15.1, 19.0 Hz); ¹³ C _{-NMR (100MHz, (CD 3)} 2 CO): δ13.9,16.3,132.9,135.6; 29 Si-NMR (79MHz, (CD 3) 2 CO): δ-21.2; IR ^(solid, cm -1): 3195,3055,2947,2868,2871 1464,1408,1007,960,874,831,706.
Example 1

A 500 mL three-necked flask equipped with a stirrer, a dropping funnel and a Dimroth condenser was replaced with argon, and 11.8 g (76.3 mmol) of 1,1-dichloro-1-silacyclopentane and 16.7 g (165 mmol) of triethylamine were placed in the flask. And 200 mL of dehydrated diethyl ether. From a dropping funnel, a solution of 10.0 g (75.7 mmol) of isopropylvinylsilanediol (Compound C) in 150 mL of dehydrated diethyl ether was added dropwise over 2 hours, and then heated to reflux for 2 hours. The reaction mixture was transferred to a separatory funnel, extracted with hexane, and washed three times with distilled water. The organic layer was dried over magnesium sulfate, filtered, and concentrated using a rotary evaporator. The obtained oily substance was distilled under reduced pressure using a Kugelrohr distillation apparatus (distillation temperature 135 ° C./40 Pa) to obtain 4,4,8,8-di (1,4-butanediyl) -2,6. -9.84 g (yield: 60.8%, GC purity: 93%) of diisopropyl-2,6-divinylcyclotetrasiloxane (compound D) as a colorless liquid was obtained. The resulting product was a mixture of cis and trans isomers based on the configuration of isopropyl and vinyl groups.
EI-MS (70 eV) m / z (relative intensity,%): 385 ([M- ⁱ Pr] ⁺ , 100), 357 (19), 343 (30), 329 (7), 315 (6); ¹ H-NMR (400 MHz, CDCl ₃ ): δ 0.48 to 0.55 (m, 8H), 0.81 to 0.84 (m, 2H) 0.94 to 1.01 (m, 12H), 57-1.61 (m, 8H), 5.81-6.06 (m, 6H); ¹³ C-NMR (mixture, 100 MHz, CDCl ₃ ): δ 11.33 (methylene, cis isomer), 11. 41 (methylene, trans isomer), 11.49 (methylene, cis isomer), 14.12 (methine, duplication), 16.47 (methyl, duplication), 24.87 (methylene, cis isomer), 24 90 (methylene, trans isomer), 24. 92 (methylene, cis isomer) 133.74, 133.81, 134.32, 134.38; ²⁹ Si-NMR (79 MHz, CDCl ₃ ): δ-33.6 (overlapping), −4.13, − 4.11; IR (neat, cm ⁻¹ ): 3054, 3012, 2943, 2927, 2866, 1596, 1464, 1406, 1250, 1076, 1057, 1009, 881, 854, 708, 681.
(Reference Example 3)

In a three-necked flask equipped with a Liebig condenser, a thermometer, a stirrer and a dropping funnel, 12.1 g (0.130 mol) of aniline, 2.33 g (0.129 mol) of water, 200 mL of diethyl ether and 30 mL of acetone were added. I stored it. The reaction vessel was cooled to 2 ° C. in an ice bath, and 10.1 g of 1,1-dichloro-1-silacyclopentane was added from the dropping funnel over 1 hour (synthesized according to the method described in Organometallics, 25, 1188, 2006, 0 .651 mol) in 85 mL of dehydrated diethyl ether was added dropwise. The precipitated solid was filtered off, and the solution was concentrated and dried under reduced pressure to obtain 6.84 g (yield 90%) of 1-silacyclopentane-1,1-diol (compound E) as colorless crystals.
¹ H-NMR (400 MHz, (CD ₃ ) ₂ CO): δ 0.42 to 0.46 (m, 4H), 1.54 to 1.58 (m, 4H), 5.07 (s, 2H); ¹³ C-NMR (100 MHz, (CD ₃ ) ₂ CO): δ 11.0, 25.0; ²⁹ Si-NMR (79 MHz, (CD ₃ ) ₂ CO): δ-9.16; IR (solid, cm ^{− 1} ) 3143, 2931, 2854, 1248, 1159, 1076, 1012, 891, 862, 781, 692.
(Example 2)

A 500 mL three-necked flask equipped with a stirrer, a dropping funnel and a Dimroth condenser was replaced with argon, and 14.5 g (85.5 mmol) of dichloroisopropylvinylsilane (Compound B), 17.1 g (169 mmol) of triethylamine and dehydrated diethyl ether were added to the flask. Contains 200 mL. From a dropping funnel, a solution of 13.5 g of 1-silacyclopentane-1,1-diol (Compound E, 115 mmol) in 150 mL of dehydrated diethyl ether was added dropwise over 2 hours and stirred at reflux for 2 hours. The reaction mixture was transferred to a separatory funnel, extracted with hexane, and washed three times with distilled water. The organic layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure using a rotary evaporator. The obtained oily substance was distilled under reduced pressure using a Kugelrohr distillation apparatus (distillation temperature 135 ° C./40 Pa) to obtain 2,2,6,6-di (1,4-butanediyl) -4,8. -Diisopropyl-4,8-divinylcyclotetrasiloxane (compound D) was obtained as a colorless liquid, 8.90 g (yield: 48.6%). The resulting product was a mixture of cis- and trans-isomers based on the configuration of isopropyl and vinyl groups. When EI-MS, ¹ H-NMR, ¹³ C-NMR, ²⁹ Si-NMR and IR spectrum were measured in the same manner as in Example 3, all the results were consistent with Example 1.
(Example 3)

A 1 L three-necked flask equipped with a stirrer, a dropping funnel and a Dimroth condenser was replaced with argon, and 14.1 g of 1,1-dichlorosilacyclobutane (manufactured by Aldrich, 100 mmol), 22.1 g (218 mmol) of triethylamine and dehydration were added to the flask. 280 mL of diethyl ether was stored. From a dropping funnel, a solution of 13.3 g (101 mmol) of isopropylvinylsilanediol (Compound C) in 200 mL of dehydrated diethyl ether was added dropwise over 3 hours and stirred for 2 hours. The reaction mixture was transferred to a separatory funnel, extracted with hexane, and washed three times with distilled water. The organic layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure using a rotary evaporator. The obtained mixture was distilled under reduced pressure using a Kugelrohr distillation apparatus (distillation temperature 120 ° C./40 Pa), whereby 4,4,8,8-di (1,3-propanediyl) -2,6 -16.5 g (yield: 82.6%, GC purity: 92%) of diisopropyl-2,6-divinylcyclotetrasiloxane (compound E) as a colorless liquid was obtained. The resulting product was a mixture of cis and trans isomers based on the configuration of isopropyl and vinyl groups.
EI-MS (70 eV) m / z (relative intensity,%): 385 ([M-Me] ⁺ , 2), 357 ([M- ⁱ Pr] ⁺ , 100); ¹ H-NMR (400 MHz, CDCl ₃ ): Δ 0.82 to 0.89 (m, 2H) 0.99 (dd, 12H, J = 7.2, 7.2 Hz), 1.39 to 1.46 (m, 8H), 1.60 1.68 (m, 4H), 5.85 to 6.09 (m, 6H); ¹³ C-NMR (100 MHz, CDCl ₃ ): δ 10.62, 10.84, 14.06, 14.21, 16 37, 16.44, 23.43, 23.69, 133.33, 133.38, 133.67, 134.53, 134.66, 134.72; ²⁹ Si-NMR (79 MHz, CDCl ₃ ): δ-36.3, -33.3, -33.2, -33.0; IR ^neat, cm -1): 3055,2976,2945,2867,1464,1406,1126,1057,1007,960,914,883,715,646.
Example 4

A 500 mL three-necked flask equipped with a stir bar and a Dimroth condenser was replaced with argon, and 300 mL of dehydrated hexane, 9.80 g (61.1 mmol) of dimethoxyisopropylvinylsilane and 1,1,3,3-tetramethyldisiloxane were added to the flask. 19 g (61.0 mmol) was stored. A 2 mL dehydrated toluene solution of 5.1 mg (10.4 μmol, 17.1 mmol%) of tris (pentafluorophenyl) borane was added dropwise from a syringe over 5 minutes. The reaction mixture was stirred at 25 ° C. for 1 hour, 12 g of alumina was added, and the mixture was stirred for 5 minutes, and filtered by suction filtration. The filtrate was distilled off under reduced pressure using a rotary evaporator and distilled under reduced pressure (boiling point 76 ° C./3.3 kPa) to obtain 4,4,6,6-tetramethyl-2-isopropyl-2. -6.58 g (yield: 41.2%, GC purity: 99%) of vinylcyclotrisiloxane (compound F) as a colorless liquid was obtained.
EI-MS (70eV) m / z ( relative _{^{intensity,%): 247 ([M}} -CH 3] +, 4), 219 ([M- i Pr] +, 100), 203 (10), 193 (20 ), 177 (5); ¹ H-NMR (400 MHz, CDCl ₃ ): δ 0.17 (s, 6H), 0.19 (s, 6H), 0.81 to 0.90 (m, 1H) 00 (d, 6H, J = 7.1 Hz), 5.87 to 6.08 (m, 3H); ¹³ C-NMR (100 MHz, CDCl ₃ ): δ 0.79, 0.86, 14.1, 16 ^29, 133.8, 134.5; ²⁹ Si-NMR (79 MHz, CDCl ₃ ): δ-8.02; IR (neat, cm ⁻¹ ): 3057, 2960, 2948, 2898, 2867, 1595, 1465 1401, 1259, 1000.
(Example 5)

A 100 mL three-necked flask equipped with a stir bar and a Dimroth condenser was replaced with argon, 50 mL of dehydrated hexane, 2.56 g (16.0 mmol) of dimethoxyisopropylvinylsilane, and 3.03 g of 1,1,3,3-tetraethyldisiloxane (Tetrahedron). Letters, 50, 7166, synthesized according to the method described in 2009, 15.9 mmol). A 1.5 mL dehydrated toluene solution of 40.2 mg (79.5 μmol, 0.5 mol%) of tris (pentafluorophenyl) borane was added dropwise over 5 minutes from a syringe. The mixture was stirred at 25 ° C. for 1 hour, added with 2 g of alumina, stirred for 5 minutes, and filtered by suction filtration. The filtrate was distilled off under reduced pressure using a rotary evaporator and distilled under reduced pressure (boiling point 70 ° C./40 Pa) to obtain 4,4,6,6-tetraethyl-2-isopropyl-2-vinylcyclotrisiloxane. 4.54 g (yield: 89.7%, GC purity: 99%) of (Compound F) was obtained as a colorless liquid.
EI-MS (70 eV) m / z (relative intensity,%): 289 ([M-Et] ⁺ , 35), 275 ([M- ⁱ Pr] ⁺ , 100) 261 (18), 247 (86), 233 (17); ¹ H-NMR (400 MHz, CDCl ₃ ): δ 0.596 (q, 4H, J = 7.8 Hz), 0.617 (q, 4H, J = 7.8 Hz), 0.82 0.93 (m, 1H), 0.964 (t, 6H, J = 7.8 Hz), 0.997 (t, 6H, J = 7.8 Hz), 1.008 (d, 6H, J = 7) .0 Hz), 5.915 (dd, 1 H, J = 10.5, 14.2 Hz), 6.049 (d, 1 H, J = 14.3 Hz), 6.054 (d, 1 H, J = 10. ^{4Hz); 13 C-NMR (} 100MHz, CDCl 3): δ6.16,6.22,7.28,7.44 ^{14.4,16.2,133.9,134.5; 29 Si-NMR (79MHz} , CDCl 3): δ-25.1, -8.62; IR (neat, cm -1): 3054,2958 2916, 2879, 2870, 1461, 1408, 1241, 999.
(Reference Example 4)

A 200 mL three-necked flask equipped with a dropping funnel, a stirrer, and a Liebig condenser was replaced with argon, and the flask was charged with 80 mL of THF and 4.33 g of palladium activated carbon (manufactured by NEM Chemcat) (5 wt% Pd, dried product). 04 mmol Pd) and 7.34 g (407 mmol) of distilled water. While cooling the reaction vessel in a water bath, 7.59 g (40.7 mmol) of 1,1,3,3-di (1,4-butanediyl) disiloxane was added dropwise from a syringe over 10 minutes and stirred for 2 hours. Insoluble matter in the reaction mixture was filtered off using a glass filter. This was concentrated under reduced pressure to obtain 8.67 g of 1,1,3,3-di (1,4-butanediyl) disiloxane-1,3-diol (Compound G) as a colorless semi-solid (yield: 97.5%, GC purity: 96%).
EI-MS (70 eV) m / z (relative intensity,%): 218 (M ⁺ , 13), 190 ([M-CH ₂ CH ₃ ] ⁺ , 32), 162 ([M-CH ₂ CH ₂ CH ₂ CH ₂ ] ⁺ , 100), 134 (31), 121 (38); ¹ H-NMR (400 MHz, (CD ₃ ) ₂ CO): δ 0.46 to 0.50 (m, 8H), 1.56 to 1.59 (m, 8H), 5.32 (s, 2H); ¹³ C-NMR (100 MHz, (CD ₃ ) ₂ CO): δ 12.0, 25.7; ²⁹ Si-NMR (79 MHz, (CD ₃ ) ₂ CO): δ 1.71; IR (solid, cm ⁻¹ ): 3276, 2725, 2857, 1249, 1076, 1051, 1014, 868, 854.
(Example 6)

A 300 mL three-necked flask equipped with a stirrer, a dropping funnel and a Dimroth condenser was replaced with argon, and 230 mL of dehydrated THF, 6.49 g (64.0 mmol) of triethylamine and 5.44 g of dichloroisopropylvinylsilane (Compound B, 32.0 mmol) were added to the flask. Was stored. From a dropping funnel, a 70 mL dehydrated THF solution of 7.00 g (Compound G, 32.0 mmol) of 1,1,3,3-di (1,4-butanediyl) disiloxane-1,3-diol was dropped over 5 minutes, Thereafter, the mixture was stirred at 25 ° C. for 1.5 hours. The reaction mixture was transferred to a separatory funnel, extracted with 100 mL of hexane, washed 3 times with 50 mL of distilled water, and dried over magnesium sulfate. This was filtered and concentrated, purified by column chromatography (stationary phase: silica gel, mobile phase: hexane), and the fraction was distilled under reduced pressure (distillation temperature 110 ° C./50 Pa) using a Kugelrohr distillation apparatus. , 4,4,6,6-di (butane-1,4-diyl) -2-isopropyl-2-vinylcyclotrisiloxane (Compound H) as a colorless liquid, 1.23 g (yield: 12.2%, GC purity: 98%).
EI-MS (70 eV) m / z (relative intensity,%): 314 (M ⁺ , 0.4) 385 ([M ⁱ Pr] ⁺ , 100), 259 (2), 243 (2), 215 ( 13); ¹ H-NMR (400 MHz, CDCl ₃ ): δ 0.53 to 0.59 (m, 8H), 0.84 to 0.92 (m, 1H) 1.00 (d, 6H, J = 6) .7 Hz), 1.60 to 1.64 (m, 8H), 6.00 (m, 3H); ¹³ C-NMR (100 MHz, CDCl ₃ ): δ 11.1, 11.2, 14.0, 16 0.0, 24.6, 24.7, 133.2, 134.9; ²⁹ Si-NMR (79 MHz, CDCl ₃ ): δ-23.6, 7.73; IR (neat, cm ⁻¹ ): 2941 , 2897, 2866, 1249, 1076, 1002.
(Example 7)

A 500 mL three-necked flask equipped with a stirrer, a dropping funnel and a Dimroth condenser was replaced with argon, and 300 mL of dehydrated hexane, 11.3 g (69.7 mmol) of dimethoxyisopropylvinylsilane and 1,1,3,3-di (1 , 4-butanediyl) disiloxane 13.0 g (69.7 mmol). A solution of tris (pentafluorophenyl) borane (106 mg, 0.209 mmol, 0.3 mol%) in 5 mL of dehydrated toluene was added dropwise from a syringe over 5 minutes. The mixture was stirred at 25 ° C. for 1 hour, added with 13 g of alumina, stirred for 5 minutes, and filtered by suction filtration. The filtrate was concentrated using a rotary evaporator and distilled under reduced pressure (boiling point 85 ° C./75 Pa) to obtain 4,4,6,6-di (butane-1,4-diyl) -2-isopropyl-2. -17.1 g (yield: 77.6%, GC purity: 99%) of vinylcyclotrisiloxane (Compound H) was obtained as a colorless liquid. When EI-MS, ¹ H-NMR, ¹³ C-NMR, ²⁹ Si-NMR and IR spectrum were measured in the same manner as in Example 10, the results were all consistent with Example 6.
(Reference Example 5)

A 500 mL three-necked flask equipped with a stirrer, a dropping funnel and a Liebig condenser was replaced with argon, and 180 mL of dehydrated THF and 20.0 g (118 mmol) of dichloroisopropylvinylsilane were stored. From a dropping funnel, a solution of 8.49 g (116 mmol) of diethylamine and 12.2 g (120 mmol) of triethylamine in 120 mL of dehydrated THF was added dropwise at −10 ° C. over 2 hours, and then stirred at 25 ° C. for 1.5 hours. To this reaction mixture, 5.83 g (153 mmol) of lithium aluminum hydride was added at 0 ° C., and the mixture was stirred for 1 hour. The reaction mixture was poured into 1500 mL of 1M hydrochloric acid in an Erlenmeyer flask with stirring and stirred for 1 hour. The reaction mixture was transferred to a separatory funnel, extracted with 100 mL of hexane, washed 5 times with 30 mL of distilled water, and then dried over magnesium sulfate. This was filtered and concentrated, and distilled under reduced pressure (boiling point 65 ° C./5.3 kPa) to obtain 8.72 g of 1,3-diisopropyl-1,3-divinyldisiloxane (Compound I) as a colorless liquid ( (Yield: 70.1%, GC purity: 98%).
EI-MS (70 eV) m / z (relative intensity,%): 186 ([M-CH ₂ = CH ₂ ] ⁺ , 3), 171 ([M- ⁱ Pr] ⁺ , 83), 143 (100), 129 (53), 115 (34); ¹ H-NMR (400 MHz, CDCl ₃ : δ 0.89 to 0.97 (m, 14H), 4.52 to 4.54 (m, 2H), 5.86 to ^{7.26 (m, 6H); 13} C-NMR (100MHz, CDCl 3): δ14.1,16.4,134.5,134.9; 29 Si-NMR (79MHz, CDCl 3): δ-8 ^{.34; IR (neat, cm -1} ): 3053,2945,2893,2866,2119,1592,1464,1402,1385,1365,1365,1240,1082,1056,1005,958,920, 79.
(Reference Example 6)

A 100 mL three-necked flask equipped with a stirrer, a dropping funnel and a Dimroth condenser was replaced with argon, and 50 mL of dehydrated dichloromethane and 3.97 g (17.1 mmol) of trichloroisocyanuric acid were placed in the flask. From a dropping funnel, a solution of 4.99 g of 1,3-diisopropyl-1,3-divinyldisiloxane (Compound I, 23.3 mmol) in 5 mL of dehydrated dichloromethane was added dropwise at 25 ° C. over 15 minutes. The progress of the reaction was followed by gas chromatography, and trichloroisocyanuric acid was added little by little until the reaction was completed. The reaction mixture was filtered through a Schlenk tube equipped with a sintered glass filter under an argon atmosphere, and the filtrate was concentrated and distilled under reduced pressure (boiling point 63 ° C./400 Pa) to give 1,3-dichloro-1,3. -3.50 g (yield: 53.3%, GC purity: 99%) of diisopropyl-1,3-divinyldisiloxane (compound J) as a colorless liquid was obtained.
EI-MS (70 eV) m / z (relative intensity,%): 239 ([M- ⁱ Pr] ⁺ , 200), 211 (89), 197 (29), 185 (17), 157 (37); ¹ H-NMR (400 MHz, CDCl ₃ ): δ 1.04 to 1.16 (m, 7H), 6.05 to 6.21 (m, 3H); ¹³ C-NMR (100 MHz, CDCl ₃ ): δ 16.00 , 16.03, 16.47, 131.57, 131.58, 136.87; ²⁹ Si-NMR (79 MHz, CDCl ₃ ): δ-7.19; IR (neat, cm ⁻¹ ): 3064, 2951 , 2870, 1597, 1464, 1406, 1387, 1271, 1248, 1086, 1061, 1001, 968, 922.
(Example 8)

A 100 mL three-necked flask equipped with a stirrer, a dropping funnel and a Liebig condenser was replaced with argon, and the flask was dehydrated THF 40 mL, triethylamine 2.51 g (24.8 mmol), 1,3-dichloro-1,3-diisopropyl-1, 3.50 g (Compound J, 12.4 mmol) of 3-divinyldisiloxane was contained. From a dropping funnel, a solution of 1.47 g of 1-silacyclopentane-1,1-diol (Compound E, 12.4 mmol) in 10 mL of dehydrated THF was added dropwise at 0 ° C. over 20 minutes, and then stirred at 25 ° C. for 3 hours. The reaction mixture was transferred to a separatory funnel, extracted with 50 mL of hexane, washed 4 times with 30 mL of distilled water, and then dried over magnesium sulfate. This was filtered, concentrated, and distilled under reduced pressure using a Kugelrohr distillation apparatus (distillation temperature 105 ° C./400 Pa) to give 6,6- (1,4-butanediyl) -2,4-diisopropyl-2, As a colorless liquid, 2.89 g (yield: 70.9%, GC purity: 98%) of 4-divinylcyclotrisiloxane (compound K) was obtained. The resulting product was a mixture of cis and trans isomers based on the configuration of isopropyl and vinyl groups.
EI-MS (70 eV) m / z (%): 328 (M ⁺ , 0.7) 285 ([M- ⁱ Pr] ⁺ , 100), 257 (43), 243 (28), 229 (11); ¹ H-NMR (400 MHz, CDCl ₃ ): δ 0.56 to 0.60 (m, 4H), 0.87 to 1.04 (m, 14H) 1.61 to 1.65 (m, 4H), 5 .88 to 6.10 (m, 6H); ¹³ C-NMR (100 MHz, CDCl ₃ ): δ 11.12, 11.24, 14.11, 14.17, 16.12, 16.14, 16.17 , 24.61, 24.64, 133.22, 133.29, 134.89, 134.97; ²⁹ Si-NMR (79 MHz, CDCl ₃ ): δ-23.9, −23.8, 7.70. ^{, 7.78; IR (neat, cm} -1): 3057,2 44,2894,2865,1594,1463,1403,1000.
(Reference Example 7)

A 500 mL three-necked flask equipped with a stirrer, a dropping funnel and a Liebig condenser was replaced with argon, and 6.01 g (59.3 mmol) of triethylamine and 10.0 g (compound B, 59.1 mmol) of dichloroisopropylvinylsilane and dehydrated tetrahydrofuran were added to the flask. Contains 100 mL. A solution of 300 mL of dehydrated THF was added dropwise from 3.49 g of 1-silacyclopentane-1,1-diol (Compound E, 29.6 mmol) to the dropping funnel over 3 hours, and then stirred at 25 ° C. for 2.5 hours. Next, 6.07 g (60.0 mmol) of triethylamine was added to the flask, and a solution of 265 mg (14.8 mmol) of distilled water in 20 mL of dehydrated THF was added dropwise from the dropping funnel over 15 minutes, followed by further stirring for 15 minutes. Again, 20 mL of dehydrated THF in 5.00 g (277 mmol) of distilled water was added dropwise to the dropping funnel over 1 hour, followed by stirring for 1.5 hours. The reaction mixture was transferred to a separatory funnel, extracted with 100 mL of hexane, washed 4 times with 30 mL of distilled water, and then dried over anhydrous magnesium sulfate. This was filtered and concentrated, purified by column chromatography (stationary phase: silica gel, mobile phase: hexane), and the fraction was distilled under reduced pressure (distillation temperature 85 ° C./40 Pa) to give 6,6- (1 , 4-butanediyl) -2,4-diisopropyl-2,4-divinylcyclotrisiloxane (compound K) as a colorless liquid, 5.87 g (yield: 60.4%, GC purity: 98%) was obtained. The resulting product was a mixture of cis and trans isomers based on the configuration of isopropyl and vinyl groups. When EI-MS, ¹ H-NMR, ¹³ C-NMR, ²⁹ Si-NMR and IR spectrum were measured in the same manner as in Example 14, the results were all consistent with Example 8.

Film Formation For Examples 10 to 24 and Comparative Examples 1 and 2, a parallel plate capacitively coupled PECVD apparatus in which the counter electrode shown in FIG. 1 is arranged on the upper side (3) and the lower side (4) is used. The silicon wafer used as (2) was installed, the system was depressurized with a vacuum pump (7), and the raw material was bubbled with helium gas introduced into the raw material container (6) installed in the thermostat (5). The raw material was supplied by the method of supplying to the chamber (1) to form a film. The chamber was kept at 150 ° C. for film formation. An RF power source (9) output with a power frequency of 13.56 MHz was set to a predetermined value, and film formation was performed for a predetermined time.

Measurement of film thickness and relative dielectric constant The film thickness of the insulating film formed on the silicon substrate was measured using an ellipsometer (model: MEL-30S) manufactured by JASCO Corporation. The dielectric constant is obtained by forming an aluminum electrode on the insulating film by vapor deposition, and then using a parameter analyzer (model: 4200-SCS type) manufactured by KEYITHLEY and an impedance analyzer (model: SOLARTRON 1260) manufactured by Solartron. The capacitance of 2 kHz was measured, and the relative dielectric constant was calculated.

Elastic modulus and hardness measurement Elastic modulus and hardness were measured by a nano indentation method using a nano indenter (model: NanoIndenter G200) manufactured by Agilent. A calibration curve was prepared using a Berkovich type indenter and fused quartz as a reference sample. The measurement was performed with an indentation depth of 10% with respect to the film thickness.

  Table 1 shows the film formation conditions shown in the above method, the thickness of the produced film, the film formation speed, the hardness, the elastic modulus, and the relative dielectric constant.

  Membranes prepared using Compound 8 of Examples 17 to 19 were prepared from 2,4,6-triisopropyl-2,4,6-trivinylcyclotrisiloxane, which is the cyclic 6-membered ring of Comparative Examples 1 and 2. The film is formed more quickly than the film formed by using it, has a high elastic modulus, and is suitable as an interlayer insulating film.

1. 1. PECVD chamber Substrate 3. Upper electrode 4. Lower electrode 5. 5. Thermostatic bath 6. Raw material container Vacuum pump8. 8. Matching circuit RF power supply 10. Earth 11. Heater 12. Mass flow controller 13. Helium gas

Claims (13)

General formula (1)

(In the formula, R ¹ represents an alkyl group having 3 to 5 carbon atoms. R ² and R ³ each independently represent an alkyl group having 1 to 3 carbon atoms. R ² and R ³ are combined together. A cyclic siloxane compound represented by the following formula: n, m and o are each independently 1 or 2, and n + m + o = 4 may be formed. The cyclic siloxane compound according to claim 1, wherein R ¹ is an isopropyl group, and R ² and R ³ are combined to form a butane-1,4-diyl group.   The cyclic siloxane compound according to claim 1 or 2, wherein m and n are 1 and o is 2.   The cyclic siloxane compound according to claim 1 or 2, wherein m and o are 1 and n is 2.   The cyclic siloxane compound according to claim 1 or 2, wherein n and o are 1 and m is 2. General formula (2)

(Wherein R ¹ represents an alkyl group having 3 to 5 carbon atoms) and a general formula (3)

(In the formula, R ² and R ³ each independently represents an alkyl group having 1 to 3 carbon atoms. R ² and R ³ may together form an alkylene group having 3 to 6 carbon atoms. The method for producing a cyclic siloxane compound according to claim 1, wherein X ¹ represents a halogen atom. General formula (4)

(Wherein R ¹ represents an alkyl group having 3 to 5 carbon atoms, X ² represents a halogen atom), and a general formula (5)

(In the formula, R ² and R ³ each independently represents an alkyl group having 1 to 3 carbon atoms. R ² and R ³ may together form an alkylene group having 3 to 6 carbon atoms. The method for producing a cyclic siloxane compound according to claim 1, 2 or 3, wherein a dialkylsilane represented by formula (1) is reacted. General formula (4)

(Wherein R ¹ represents an alkyl group having 3 to 5 carbon atoms, X ² represents a halogen atom), and a general formula (6)

(In the formula, R ² and R ³ each independently represents an alkyl group having 1 to 3 carbon atoms. R ² and R ³ may together form an alkylene group having 3 to 6 carbon atoms. 6. The method for producing a cyclic siloxane compound according to claim 1, 2 or 5, wherein the dihydroxydisiloxane represented by formula (1) is reacted. General formula (7) in the presence of Lewis acid

(Wherein R ¹ represents an alkyl group having 3 to 5 carbon atoms. Two R ^{4 s} are the same or different and are a hydrogen atom or a methyl group) and a general formula (8)

(In the formula, R ² and R ³ each independently represents an alkyl group having 1 to 3 carbon atoms. R ² and R ³ may together form an alkylene group having 3 to 6 carbon atoms. 6. The method for producing a cyclic siloxane compound according to claim 1, 2 or 5, wherein the dihydrodisiloxane represented by formula (1) is reacted. General formula (5)

(In the formula, R ² and R ³ each independently represents an alkyl group having 1 to 3 carbon atoms. R ² and R ³ may together form an alkylene group having 3 to 6 carbon atoms. )) And a general formula (9)

(Wherein R ¹ represents an alkyl group having 3 to 5 carbon atoms, and X ³ represents a halogen atom). 4. A method for producing a cyclic siloxane compound according to 4.   6. A method for producing an electrical insulating film, wherein the cyclic siloxane compound according to claim 1 is used as a precursor of a plasma enhanced chemical vapor deposition method.   An electrical insulating film produced by using the cyclic siloxane compound according to any one of claims 1 to 5 as a precursor of a plasma enhanced chemical vapor deposition method.   A semiconductor electronic device using the electrical insulating film according to claim 12.

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