JP2014065699A - Method for producing cyclic siloxane compound, and disiloxane compound - Google Patents

Method for producing cyclic siloxane compound, and disiloxane compound Download PDF

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JP2014065699A
JP2014065699A JP2012252735A JP2012252735A JP2014065699A JP 2014065699 A JP2014065699 A JP 2014065699A JP 2012252735 A JP2012252735 A JP 2012252735A JP 2012252735 A JP2012252735 A JP 2012252735A JP 2014065699 A JP2014065699 A JP 2014065699A
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divinyldisiloxane
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JP6131575B2 (en
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Teppei Hayakawa
哲平 早川
Kazuhisa Kono
和久 河野
Yoichi Chiba
洋一 千葉
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Tosoh Corp
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    • C—CHEMISTRY; METALLURGY
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    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
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    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
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    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/02126—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
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    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
    • H01L21/02208—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
    • H01L21/02214—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and oxygen
    • H01L21/02216—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and oxygen the compound being a molecule comprising at least one silicon-oxygen bond and the compound having hydrogen or an organic group attached to the silicon or oxygen, e.g. a siloxane
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    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
    • H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H01L21/02274—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition in the presence of a plasma [PECVD]

Abstract

PROBLEM TO BE SOLVED: To provide a method of efficiently producing, from dialkoxy alkyl vinyl silane compounds, cyclic tetramers, particularly, 2,4,6,8-tetraalkyl-2,4,6,8-tetravinylcyclotetrasiloxane.SOLUTION: A cyclic siloxane compound represented by the specified general formula (3) is produced by reacting a dialkoxy alkyl vinyl silane compound with water in the coexistence of an acid or a base to produce a disiloxane compound, and then reacting it in the coexistence of an acid or a base.

Description

本発明は、効率よく製造できる環状シロキサン化合物の製造方法および該製造方法における中間体であるジシロキサン化合物に関するものである。   The present invention relates to a method for producing a cyclic siloxane compound that can be produced efficiently, and a disiloxane compound that is an intermediate in the production method.

近年の半導体素子の高集積化に伴い、ＬＳＩ配線として従来のＡｌから低抵抗でマイグレーション耐性に優れるＣｕが用いられるようになり、一方で層間絶縁膜としては従来の酸化シリコン膜（ＳｉＯ２膜）から、より低誘電率の層関絶縁膜（Ｌｏｗ−ｋ膜）が検討されている。 With the recent high integration of semiconductor elements, Cu, which has low resistance and excellent migration resistance, has been used as an LSI wiring from conventional Al, while a conventional silicon oxide film (SiO 2 film) is used as an interlayer insulating film. Therefore, a layered dielectric film (Low-k film) having a lower dielectric constant has been studied.

現在、層間絶縁膜の形成方法としては、プラズマ化学気相成長法（ＰＥＣＶＤ法）が主に用いられている。これまでに環状シロキサンを、分子内ポアを有する前駆体（プレカーサー）として用いて、低ｋ値の膜を成膜する検討がなされている。例えば蒸気圧が低い環状シロキサン化合物に、重合基であるビニル基を結合させることで、成膜速度を速くすることに成功している（例えば特許文献１参照）。   At present, plasma chemical vapor deposition (PECVD) is mainly used as a method for forming an interlayer insulating film. So far, studies have been made to form a film having a low k value using cyclic siloxane as a precursor (precursor) having an intramolecular pore. For example, it has succeeded in increasing the film-forming speed | rate by combining the vinyl group which is a polymeric group with the cyclic siloxane compound with a low vapor pressure (for example, refer patent document 1).

前述の環状シロキサン化合物において、ＰＥＣＶＤ法のプレカーサーとして最適な環サイズは、低ｋ値を達成できること、および蒸気圧を考慮すると６員環または８員環である。蒸気圧の面では分子量の小さい６員環が好ましいが、低ｋ値に寄与する分子内ポアの大きさを考慮すると８員環が好ましい。特許文献１においてジアルコキシアルキルビニルシラン化合物を原料とし、６員環の環状シロキサン化合物を得る方法は記載されているが、効率よく製造できる８員環の環状シロキサン化合物の製造方法については見出されていない。   In the cyclic siloxane compound described above, the optimum ring size as a precursor for the PECVD method is a 6-membered ring or an 8-membered ring in consideration of the ability to achieve a low k value and vapor pressure. In terms of vapor pressure, a 6-membered ring having a small molecular weight is preferable, but an 8-membered ring is preferable in consideration of the size of an intramolecular pore contributing to a low k value. Patent Document 1 describes a method of obtaining a 6-membered cyclic siloxane compound using a dialkoxyalkylvinylsilane compound as a raw material, but has found a method for producing an 8-membered cyclic siloxane compound that can be efficiently produced. Absent.

特開２００５−５１１９２号公報JP 2005-51192 A

本発明はジアルコキシアルキルビニルシラン化合物から８員環環状シロキサン、特に２，４，６，８−テトラアルキル−２，４，６，８−テトラビニルシクロテトラシロキサンを効率的に製造する方法を提供することを目的とする。   The present invention provides a method for efficiently producing 8-membered cyclic siloxanes, especially 2,4,6,8-tetraalkyl-2,4,6,8-tetravinylcyclotetrasiloxane, from dialkoxyalkylvinylsilane compounds. For the purpose.

本発明者らは、ジアルコキシアルキルビニルシラン化合物を酸または塩基共存下、水と反応させることで一旦ジシロキサン化合物を製造し、次いで水層を除去して非水条件下としたのち、酸または塩基を添加し反応させることで、目的のシクロテトラシロキサン化合物が効率的に得られることを見出し、本発明を完成するにいたった。   The inventors of the present invention once produced a disiloxane compound by reacting a dialkoxyalkylvinylsilane compound with water in the presence of an acid or a base, and then removed the aqueous layer to obtain non-aqueous conditions. It was found that the target cyclotetrasiloxane compound can be efficiently obtained by adding and reacting, and the present invention was completed.

すなわち本発明は、以下のとおりである。
［１］下記一般式（１） That is, the present invention is as follows.
[1] The following general formula (1)

Figure 2014065699
Figure 2014065699

（式中、Ｒ１、Ｒ２は炭素数１〜３の直鎖または分岐鎖のアルキル基を示す。）で表されるジアルコキシアルキルビニルシラン化合物を、酸または塩基の共存下、水と反応させることにより、下記一般式（２） (Wherein R 1 and R 2 represent a linear or branched alkyl group having 1 to 3 carbon atoms), and the dialkoxyalkylvinylsilane compound represented by the above is reacted with water in the presence of an acid or a base. The following general formula (2)

Figure 2014065699
Figure 2014065699

（式中、Ｒ１は一般式（１）に同じ。Ｒ３、Ｒ４は一般式（１）のＲ２に同じかまたは水素原子を示す。）で表されるジシロキサン化合物を製造し、次いで、いったん水層を除去した後、一般式（２）で表されるジシロキサン化合物を酸または塩基の共存下、反応させることを特徴とする、下記一般式（３） (Wherein R 1 is the same as in general formula (1). R 3 and R 4 are the same as or in the hydrogen atom in R 2 of general formula (1)). Next, once the aqueous layer is removed, the disiloxane compound represented by the general formula (2) is reacted in the presence of an acid or a base, and the following general formula (3)

Figure 2014065699
Figure 2014065699

（式中、Ｒ１は一般式（１）に同じ。）で表される環状シロキサン化合物の製造方法。
［２］一般式（１）で表されるジアルコキシアルキルビニルシラン化合物を酸または塩基の共存下、水と反応させる際の反応温度が−５０〜２５℃であることを特徴とする上述の［１］に記載の製造方法。
［３］一般式（２）で表されるジシロキサン化合物を酸または塩基の共存下、反応させる反応時間が３０分（０．５時間）以上、１ヶ月（７２０時間）以下であることを特徴とする上述の［１］または［２］に記載の製造方法。
［４］酸として硫酸の共存下に反応を行うことを特徴とする上述の［１］〜［３］のいずれかに記載の製造方法。
［５］Ｒ１がイソプロピル基、Ｒ２がメチル基、Ｒ３およびＲ４がメチル基または水素原子であることを特徴とする上述の［１］〜［４］のいずれかに記載の製造方法。
［６］上述の［１］〜［５］のいずれかに記載の製造方法により製造された環状シロキサン化合物を材料として用いることを特徴とする絶縁膜。
［７］下記一般式（２）で表されることを特徴とするジシロキサン化合物。 (Wherein R 1 is the same as in general formula (1)).
[2] The above-mentioned [1], wherein the reaction temperature when the dialkoxyalkylvinylsilane compound represented by the general formula (1) is reacted with water in the presence of an acid or a base is −50 to 25 ° C. ] The manufacturing method of description.
[3] The reaction time for reacting the disiloxane compound represented by the general formula (2) in the presence of an acid or a base is 30 minutes (0.5 hours) or longer and 1 month (720 hours) or shorter. The production method according to [1] or [2] above.
[4] The production method according to any one of [1] to [3], wherein the reaction is performed in the presence of sulfuric acid as an acid.
[5] The production method according to any one of the above [1] to [4], wherein R 1 is an isopropyl group, R 2 is a methyl group, R 3 and R 4 are a methyl group or a hydrogen atom. .
[6] An insulating film characterized in that a cyclic siloxane compound produced by the production method according to any one of [1] to [5] above is used as a material.
[7] A disiloxane compound represented by the following general formula (2).

Figure 2014065699
Figure 2014065699

（式中、Ｒ１は一般式（１）に同じ。Ｒ３、Ｒ４は一般式（１）のＲ２に同じかまたは水素原子を示す。）
以下、本発明をさらに詳細に説明する。 (In the formula, R 1 is the same as in general formula (1). R 3 and R 4 are the same as R 2 in general formula (1) or a hydrogen atom.)
Hereinafter, the present invention will be described in more detail.

本発明において、一般式（１）におけるＲ１、Ｒ２は炭素数１〜３の直鎖または分岐鎖のアルキル基を示し、具体的には例えばメチル基、エチル基、ノルマルプロピル基、イソプロピル基等が挙げられる。また、Ｒ３、Ｒ４は上記Ｒ２と同じかまたは水素原子を示す。これらの中でも、最終目的物である一般式（３）で表される環状シロキサン化合物の収率の観点から、好ましくはＲ１がイソプロピル基、Ｒ２がメチル基、Ｒ３、Ｒ４はメチル基または水素原子である。 In the present invention, R 1 and R 2 in the general formula (1) represent a linear or branched alkyl group having 1 to 3 carbon atoms, and specifically include, for example, a methyl group, an ethyl group, a normal propyl group, and an isopropyl group. Etc. R 3 and R 4 are the same as R 2 or a hydrogen atom. Among these, from the viewpoint of the yield of the cyclic siloxane compound represented by the general formula (3), which is the final target product, R 1 is preferably an isopropyl group, R 2 is a methyl group, R 3 and R 4 are methyl groups. Or it is a hydrogen atom.

具体的な一般式（１）で表されるジアルコキシアルキルビニルシラン化合物としては、例えばジメトキシメチルビニルシラン、ジメトキシエチルビニルシラン、ジメトキシプロピルビニルシラン、ジメトキシイソプロピルビニルシラン、ジエトキシメチルビニルシラン、ジエトキシエチルビニルシラン、ジエトキシプロピルビニルシラン、ジエトキシイソプロピルビニルシラン、ジプロポキシメチルビニルシラン、ジプロポキシエチルビニルシラン、ジプロポキシプロピルビニルシラン、ジプロポキシイソプロピルビニルシラン、ジイソプロポキシメチルビニルシラン、ジイソプロポキシエチルビニルシラン、ジイソプロポキシプロピルビニルシラン、ジイソプロポキシイソプロピルビニルシラン等が挙げられる。   Specific examples of the dialkoxyalkylvinylsilane compound represented by the general formula (1) include dimethoxymethylvinylsilane, dimethoxyethylvinylsilane, dimethoxypropylvinylsilane, dimethoxyisopropylvinylsilane, diethoxymethylvinylsilane, diethoxyethylvinylsilane, diethoxypropyl. Vinylsilane, diethoxyisopropylvinylsilane, dipropoxymethylvinylsilane, dipropoxyethylvinylsilane, dipropoxypropylvinylsilane, dipropoxyisopropylvinylsilane, diisopropoxymethylvinylsilane, diisopropoxyethylvinylsilane, diisopropoxypropylvinylsilane, diisopropoxyisopropylvinylsilane Etc.

上記一般式（１）で表されるジアルコキシアルキルビニルシラン化合物を酸または塩基の共存下、水と反応させて、下記一般式（２）で表されるジシロキサン化合物を製造する。   The dialkoxyalkylvinylsilane compound represented by the general formula (1) is reacted with water in the presence of an acid or a base to produce a disiloxane compound represented by the following general formula (2).

Figure 2014065699
Figure 2014065699

（式中、Ｒ１は一般式（１）に同じ。Ｒ３、Ｒ４は一般式（１）のＲ２に同じかまたは水素原子を示す。）
一般式（２）におけるＲ１は一般式（１）に同じであり、Ｒ３、Ｒ４は一般式（１）のＲ２に同じかまたは水素原子を示し、好ましくはＲ１がイソプロピル基、Ｒ３、Ｒ４はメチル基または水素原子である。 (In the formula, R 1 is the same as in general formula (1). R 3 and R 4 are the same as R 2 in general formula (1) or a hydrogen atom.)
R 1 in the general formula (2) is the same as that in the general formula (1), R 3 and R 4 are the same as R 2 in the general formula (1) or a hydrogen atom, and preferably R 1 is an isopropyl group, R 3 and R 4 are a methyl group or a hydrogen atom.

具体的な一般式（２）で表される化合物としては、例えば１，３−ジヒドロキシ−１，３−ジメチル−１，３−ジビニルジシロキサン、１−ヒドロキシ−３−メトキシ−１，３−ジメチル−１，３−ジビニルジシロキサン、１−エトキシ−３−ヒドロキシ−１，３−ジメチル−１，３−ジビニルジシロキサン、１−ヒドロキシ−３−プロポキシ−１，３−ジメチル−１，３−ジビニルジシロキサン、１−ヒドロキシ−３−イソプロポキシ−１，３−ジメチル−１，３−ジビニルジシロキサン、１，３−ジメトキシ−１，３−ジメチル−１，３−ジビニルジシロキサン、１，３−ジエトキシ−１，３−ジメチル−１，３−ジビニルジシロキサン、１，３−ジプロポキシ−１，３−ジメチル−１，３−ジビニルジシロキサン、１，３−ジイソプロポキシ−１，３−ジメチル−１，３−ジビニルジシロキサン、１，３−ジヒドロキシ−１，３−ジエチル−１，３−ジビニルジシロキサン、１−ヒドロキシ−３−メトキシ−１，３−ジエチル−１，３−ジビニルジシロキサン、１−エトキシ−３−ヒドロキシ−１，３−ジエチル−１，３−ジビニルジシロキサン、１−ヒドロキシ−３−プロポキシ−１，３−ジエチル−１，３−ジビニルジシロキサン、１−ヒドロキシ−３−イソプロポキシ−１，３−ジエチル−１，３−ジビニルジシロキサン、１，３−ジメトキシ−１，３−ジエチル−１，３−ジビニルジシロキサン、１，３−ジエトキシ−１，３−ジエチル−１，３−ジビニルジシロキサン、１，３−ジプロポキシ−１，３−ジエチル−１，３−ジビニルジシロキサン、１，３−ジイソプロポキシ−１，３−ジエチル−１，３−ジビニルジシロキサン、１，３−ジヒドロキシ−１，３−ジプロピル−１，３−ジビニルジシロキサン、１−ヒドロキシ−３−メトキシ−１，３−ジプロピル−１，３−ジビニルジシロキサン、１−エトキシ−３−ヒドロキシ−１，３−ジプロピル−１，３−ジビニルジシロキサン、１−ヒドロキシ−３−プロポキシ−１，３−ジ−ｎ−プロピル−１，３−ジビニルジシロキサン、１−ヒドロキシ−３−イソプロポキシ−１，３−ジプロピル−１，３−ジビニルジシロキサン、１，３−ジメトキシ−１，３−ジプロピル−１，３−ジビニルジシロキサン、１，３−ジエトキシ−１，３−ジプロピル−１，３−ジビニルジシロキサン、１，３−ジプロポキシ−１，３−ジプロピル−１，３−ジビニルジシロキサン、１，３−ジイソプロポキシ−１，３−ジプロピル−１，３−ジビニルジシロキサン、１，３−ジヒドロキシ−１，３−ジイソプロピル−１，３−ジビニルジシロキサン、１−ヒドロキシ−３−メトキシ−１，３−ジイソプロピル−１，３−ジビニルジシロキサン、１−エトキシ−３−ヒドロキシ−１，３−ジイソプロピル−１，３−ジビニルジシロキサン、１−ヒドロキシ−３−プロポキシ−１，３−ジイソプロピル−１，３−ジビニルジシロキサン、１−ヒドロキシ−３−イソプロポキシ−１，３−ジイソプロピル−１，３−ジビニルジシロキサン、１，３−ジメトキシ−１，３−ジイソプロピル−１，３−ジビニルジシロキサン、１，３−ジエトキシ−１，３−ジイソプロピル−１，３−ジビニルジシロキサン、１，３−ジプロポキシ−１，３−ジイソプロピル−１，３−ジビニルジシロキサン、１，３−ジイソプロポキシ−１，３−ジイソプロピル−１，３−ジビニルジシロキサン等が挙げられる。   Specific examples of the compound represented by the general formula (2) include 1,3-dihydroxy-1,3-dimethyl-1,3-divinyldisiloxane and 1-hydroxy-3-methoxy-1,3-dimethyl. -1,3-divinyldisiloxane, 1-ethoxy-3-hydroxy-1,3-dimethyl-1,3-divinyldisiloxane, 1-hydroxy-3-propoxy-1,3-dimethyl-1,3-divinyl Disiloxane, 1-hydroxy-3-isopropoxy-1,3-dimethyl-1,3-divinyldisiloxane, 1,3-dimethoxy-1,3-dimethyl-1,3-divinyldisiloxane, 1,3- Diethoxy-1,3-dimethyl-1,3-divinyldisiloxane, 1,3-dipropoxy-1,3-dimethyl-1,3-divinyldisiloxane, 1,3-diisopropyl Xi-1,3-dimethyl-1,3-divinyldisiloxane, 1,3-dihydroxy-1,3-diethyl-1,3-divinyldisiloxane, 1-hydroxy-3-methoxy-1,3-diethyl- 1,3-divinyldisiloxane, 1-ethoxy-3-hydroxy-1,3-diethyl-1,3-divinyldisiloxane, 1-hydroxy-3-propoxy-1,3-diethyl-1,3-divinyldi Siloxane, 1-hydroxy-3-isopropoxy-1,3-diethyl-1,3-divinyldisiloxane, 1,3-dimethoxy-1,3-diethyl-1,3-divinyldisiloxane, 1,3-diethoxy -1,3-diethyl-1,3-divinyldisiloxane, 1,3-dipropoxy-1,3-diethyl-1,3-divinyldisiloxane, 1,3-diiso Roxy-1,3-diethyl-1,3-divinyldisiloxane, 1,3-dihydroxy-1,3-dipropyl-1,3-divinyldisiloxane, 1-hydroxy-3-methoxy-1,3-dipropyl- 1,3-divinyldisiloxane, 1-ethoxy-3-hydroxy-1,3-dipropyl-1,3-divinyldisiloxane, 1-hydroxy-3-propoxy-1,3-di-n-propyl-1, 3-divinyldisiloxane, 1-hydroxy-3-isopropoxy-1,3-dipropyl-1,3-divinyldisiloxane, 1,3-dimethoxy-1,3-dipropyl-1,3-divinyldisiloxane, , 3-Diethoxy-1,3-dipropyl-1,3-divinyldisiloxane, 1,3-dipropoxy-1,3-dipropyl-1,3-divinyldisi Loxane, 1,3-diisopropoxy-1,3-dipropyl-1,3-divinyldisiloxane, 1,3-dihydroxy-1,3-diisopropyl-1,3-divinyldisiloxane, 1-hydroxy-3- Methoxy-1,3-diisopropyl-1,3-divinyldisiloxane, 1-ethoxy-3-hydroxy-1,3-diisopropyl-1,3-divinyldisiloxane, 1-hydroxy-3-propoxy-1,3- Diisopropyl-1,3-divinyldisiloxane, 1-hydroxy-3-isopropoxy-1,3-diisopropyl-1,3-divinyldisiloxane, 1,3-dimethoxy-1,3-diisopropyl-1,3-divinyl Disiloxane, 1,3-diethoxy-1,3-diisopropyl-1,3-divinyldisiloxane, 1,3-dip Epoxy-1,3-diisopropyl-1,3-divinyl disiloxane, 1,3-diisopropoxy-1,3-diisopropyl-1,3-divinyl disiloxane and the like.

反応の際、一般式（１）で表されるジアルコキシアルキルビニルシラン化合物の反応溶媒中の濃度は特に限定されるものではなく、水層との分層性および製造効率を考慮すると０．０１ｍｏｌ／ｌ以上が好ましく、０．１〜１０ｍｏｌ／ｌが特に好ましい。   During the reaction, the concentration of the dialkoxyalkylvinylsilane compound represented by the general formula (1) in the reaction solvent is not particularly limited, and is 0.01 mol / in consideration of the separation property with the aqueous layer and the production efficiency. l or more is preferable, and 0.1-10 mol / l is especially preferable.

用いる酸または塩基は特に限定されるものではなく、例えば、塩酸、硫酸、硝酸等の無機酸；トルエンスルホン酸等の有機酸；水酸化カリウム、水酸化ナトリウム等の無機塩基；ジエチルアミン等の有機塩基を用いることができる。これらの中でも、最終目的物である一般式（３）で表される環状シロキサン化合物の収率の観点から、無機酸が好ましく特に硫酸が好ましい。   The acid or base to be used is not particularly limited. For example, inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid; organic acids such as toluenesulfonic acid; inorganic bases such as potassium hydroxide and sodium hydroxide; organic bases such as diethylamine Can be used. Among these, from the viewpoint of the yield of the cyclic siloxane compound represented by the general formula (3) which is the final target product, an inorganic acid is preferable, and sulfuric acid is particularly preferable.

酸または塩基の添加量は、特に限定されるものではなく、収率の観点からジアルコキシアルキルビニルシラン化合物１モルに対し０．０１〜１０ｍｏｌ当量が好ましく、０．１〜１ｍｏｌ当量が特に好ましい。   The addition amount of the acid or base is not particularly limited, and is preferably 0.01 to 10 mol equivalents and particularly preferably 0.1 to 1 mol equivalents with respect to 1 mol of the dialkoxyalkylvinylsilane compound from the viewpoint of yield.

反応温度は、一般式（１）で表されるジアルコキシアルキルビニルシラン化合物の濃度との兼ね合いによるので特に限定されるものではなく、−５０〜２５℃の範囲が好ましく、−２０〜０℃の範囲が特に好ましい。   The reaction temperature is not particularly limited because it depends on the concentration of the dialkoxyalkylvinylsilane compound represented by the general formula (1), and is preferably in the range of −50 to 25 ° C., and in the range of −20 to 0 ° C. Is particularly preferred.

反応時間は上述の酸または塩基の添加量および反応温度との兼ね合いにより、特に限定されるものではなく、０．５〜１０時間が好ましく、０．５〜６時間が特に好ましい。   The reaction time is not particularly limited depending on the balance between the amount of acid or base added and the reaction temperature, and is preferably 0.5 to 10 hours, particularly preferably 0.5 to 6 hours.

反応の際に、反応溶媒を使用してもよく、または使用せずに無溶媒系でもよい。反応溶媒を使用する場合、その種類は特に限定されるものではなく、例えばｎ−ペンタン、ｉ−ペンタン、ｎ−ヘキサン、シクロヘキサン、ｎ−ヘプタン、ｎ−デカン等の飽和炭化水素類；トルエン、キシレン、デセン等の不飽和炭化水素類；ジエチルエーテル、ジプロピルエーテル、ｔｅｒｔ−ブチルメチルエーテル、ジブチルエーテル、シクロペンチルメチルエーテル等のエーテル類；またはこれらの混合溶媒も使用することができる。これらの中でも水層との分層性を考慮すると飽和炭化水素類が望ましい。   In the reaction, a reaction solvent may be used, or a solventless system may be used without using it. When using a reaction solvent, the kind is not specifically limited, For example, saturated hydrocarbons, such as n-pentane, i-pentane, n-hexane, cyclohexane, n-heptane, n-decane; Toluene, xylene , Unsaturated hydrocarbons such as decene; ethers such as diethyl ether, dipropyl ether, tert-butyl methyl ether, dibutyl ether, cyclopentyl methyl ether; or a mixed solvent thereof can also be used. Among these, saturated hydrocarbons are desirable in view of the layer separation with the aqueous layer.

次に、一般式（２）で表されるジシロキサン化合物を製造した後、いったん水層を除去した後、一般式（２）で表されるジシロキサン化合物を酸または塩基の共存下、反応させ下記一般式（３）で表される環状シロキサン化合物を製造する。   Next, after manufacturing the disiloxane compound represented by the general formula (2), once removing the aqueous layer, the disiloxane compound represented by the general formula (2) is reacted in the presence of an acid or a base. A cyclic siloxane compound represented by the following general formula (3) is produced.

Figure 2014065699
Figure 2014065699

（式中、Ｒ１は一般式（１）に同じ。）
一般式（３）におけるＲ１は一般式（１）に同じであり、好ましくはＲ１がイソプロピル基である。 (In the formula, R 1 is the same as in general formula (1).)
R 1 in the general formula (3) is the same as that in the general formula (1), and preferably R 1 is an isopropyl group.

具体的な一般式（３）で表される化合物としては、例えば２，４，６，８−テトラメチル−２，４，６，８−テトラビニルシクロテトラシロキサン、２，４，６，８−テトラエチル−２，４，６，８−テトラビニルシクロテトラシロキサン、２，４，６，８−テトラプロピル−２，４，６，８−テトラビニルシクロテトラシロキサン、２，４，６，８−テトライソプロピル−２，４，６，８−テトラビニルシクロテトラシロキサン等が挙げられる。   Specific examples of the compound represented by the general formula (3) include 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane, 2,4,6,8- Tetraethyl-2,4,6,8-tetravinylcyclotetrasiloxane, 2,4,6,8-tetrapropyl-2,4,6,8-tetravinylcyclotetrasiloxane, 2,4,6,8-tetra Examples include isopropyl-2,4,6,8-tetravinylcyclotetrasiloxane.

一般式（２）で表される化合物の濃度は、０．０１ｍｏｌ／ｌ以上が好ましく、０．１〜１０ｍｏｌ／ｌが特に好ましい。   The concentration of the compound represented by the general formula (2) is preferably 0.01 mol / l or more, particularly preferably 0.1 to 10 mol / l.

用いられる酸または塩基は、前述の一般式（２）で表されるジシロキサン化合物製造に用いられる酸または塩基と同様のものを例示することができる。   Examples of the acid or base used include the same acids or bases used for producing the disiloxane compound represented by the general formula (2).

酸または塩基の濃度は、特に限定されるものではなく、収率の観点からジアルコキシアルキルビニルシラン化合物に対し０．０１〜１０ｍｏｌ当量が好ましく、０．１〜０．５ｍｏｌ当量が特に好ましい。   The concentration of the acid or base is not particularly limited, and is preferably 0.01 to 10 mol equivalents, particularly preferably 0.1 to 0.5 mol equivalents with respect to the dialkoxyalkylvinylsilane compound from the viewpoint of yield.

また、反応温度は１０〜２００℃の範囲が好ましく、反応時間は３０分（０．５時間）以上、１ヶ月（７２０時間）以下が好ましく、特に好ましくは１時間以上、２４時間以下である。   The reaction temperature is preferably in the range of 10 to 200 ° C., and the reaction time is preferably 30 minutes (0.5 hours) or longer and 1 month (720 hours) or shorter, particularly preferably 1 hour or longer and 24 hours or shorter.

反応溶媒は前述の一般式（２）で表されるジシロキサン化合物製造に用いられる溶媒と同様のものを例示することができる。   Examples of the reaction solvent include the same solvents as those used in the production of the disiloxane compound represented by the general formula (2).

このようにして得られた環状シロキサン化合物は、絶縁膜等の分子内ポア前駆体プロセスプリカーサーとして好適である。   The cyclic siloxane compound thus obtained is suitable as an intramolecular pore precursor process precursor for an insulating film or the like.

絶縁膜の製造方法としては、例えばＣＶＤ法により環状シロキサン化合物を原料として基板上に薄膜を製造することができる。その場合、環状シロキサン化合物の供給方法としては、加熱した環状シロキサン化合物に不活性キャリアガスを導入し、キャリアガスに同伴させて基板の置かれた反応槽に導く方法、環状シロキサン化合物または有機溶媒に環状シロキサン化合物を溶かした溶液を気化器に送って気化器内でガス化して基板の置かれた反応槽に導く方法等がある。   As a method for manufacturing the insulating film, for example, a thin film can be manufactured on a substrate by using a cyclic siloxane compound as a raw material by a CVD method. In that case, as a method for supplying the cyclic siloxane compound, an inert carrier gas is introduced into the heated cyclic siloxane compound, and the carrier gas is entrained in the reaction vessel where the substrate is placed. There is a method in which a solution in which a cyclic siloxane compound is dissolved is sent to a vaporizer, gasified in the vaporizer, and led to a reaction vessel on which a substrate is placed.

有機溶媒に溶かして溶液として用いる場合、有機溶媒としては、例えば、メタノール、エタノール、イソプロパノ−ル等のアルコール類；酢酸エチル、酢酸ブチル、酢酸イソアミル等のエステル類；エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル等のグリコールエーテル類；グライム、ジグライム、トリグライム、テトラヒドロフラン等のエーテル類；メチルブチルケトン、メチルイソブチルケトン、エチルブチルケトン、ジプロピルケトン、ジイソブチルケトン、メチルアミルケトン、シクロヘキサノン等のケトン類；ヘキサン、シクロヘキサン、ヘプタン、オクタン、トルエン、キシレン等の炭化水素類；等が挙げられ、特に限定されるものではない。   When used as a solution by dissolving in an organic solvent, examples of the organic solvent include alcohols such as methanol, ethanol and isopropanol; esters such as ethyl acetate, butyl acetate and isoamyl acetate; ethylene glycol monomethyl ether and ethylene glycol mono Glycol ethers such as ethyl ether and ethylene glycol monobutyl ether; ethers such as glyme, diglyme, triglyme and tetrahydrofuran; methyl butyl ketone, methyl isobutyl ketone, ethyl butyl ketone, dipropyl ketone, diisobutyl ketone, methyl amyl ketone, cyclohexanone, etc. Ketones; hydrocarbons such as hexane, cyclohexane, heptane, octane, toluene, xylene; and the like, and the like are not particularly limited.

また、ＣＶＤ法としては熱ＣＶＤ、プラズマＣＶＤ、光ＣＶＤ等一般に使用されるＣＶＤ法であれば特に限定されない。塗布熱分解法の原料塗布方法としては例えばスピンコート法、ディップ法、噴霧法等が挙げられ、加熱方法としてはオーブン、ホットプレート等が使用できるが、塗布方法、加熱方法およびその組み合せは特に限定されない。   The CVD method is not particularly limited as long as it is a commonly used CVD method such as thermal CVD, plasma CVD, or photo CVD. Examples of the raw material coating method of the coating pyrolysis method include a spin coating method, a dip method, a spraying method, and the like. As a heating method, an oven, a hot plate, or the like can be used. Not.

このように得られた絶縁膜は、層間絶縁膜（Ｌｏｗ−ｋ膜）として優れたものであり、ｋ値は２〜３が好ましく、特に好ましくは２．５〜２．９である。   The insulating film thus obtained is excellent as an interlayer insulating film (Low-k film), and the k value is preferably 2 to 3, particularly preferably 2.5 to 2.9.

本発明により、特に８員環構造を有する２，４，６，８−テトラアルキル−２，４，６，８−テトラビニルシクロテトラシロキサン化合物を、ジアルコキシアルキルビニルシランを原料に用いて、効率的に製造することができる。この８員環構造を有する環状シロキサン化合物は、分子内ポア前駆体プロセスのプレカーサーとして有用である、   According to the present invention, a 2,4,6,8-tetraalkyl-2,4,6,8-tetravinylcyclotetrasiloxane compound having an 8-membered ring structure can be efficiently produced using dialkoxyalkylvinylsilane as a raw material. Can be manufactured. The cyclic siloxane compound having this 8-membered ring structure is useful as a precursor for an intramolecular pore precursor process.

実施例２における２，４，６，８−テトライソプロピル−２，４，６，８−テトラビニルシクロテトラシロキサンへの転換率の経時変化を示す図である。FIG. 3 is a graph showing the change over time in the conversion rate to 2,4,6,8-tetraisopropyl-2,4,6,8-tetravinylcyclotetrasiloxane in Example 2. 実施例２における２，４，６，８−テトライソプロピル−２，４，６，８−テトラビニルシクロテトラシロキサンの収率の経時変化を示す図である。FIG. 4 is a graph showing the change over time in the yield of 2,4,6,8-tetraisopropyl-2,4,6,8-tetravinylcyclotetrasiloxane in Example 2. 実施例３における２，４，６，８−テトライソプロピル−２，４，６，８−テトラビニルシクロテトラシロキサンへの転換率の経時変化を示す図である。6 is a graph showing the change over time in the conversion rate to 2,4,6,8-tetraisopropyl-2,4,6,8-tetravinylcyclotetrasiloxane in Example 3. FIG. 実施例３における２，４，６，８−テトライソプロピル−２，４，６，８−テトラビニルシクロテトラシロキサンの収率の経時変化を示す図である。FIG. 4 is a graph showing the change over time in the yield of 2,4,6,8-tetraisopropyl-2,4,6,8-tetravinylcyclotetrasiloxane in Example 3. 実施例４の膜を製造した装置Apparatus for producing the membrane of Example 4 実施例５で得られた１，３−ジメトキシ−１，３−ジイソプロピル−１，３−ジビニルジシロキサンのマススペクトル測定結果である。4 is a mass spectrum measurement result of 1,3-dimethoxy-1,3-diisopropyl-1,3-divinyldisiloxane obtained in Example 5. FIG. 実施例５で得られた１−メトキシ−３−ヒドロキシ−１，３−ジイソプロピル−１，３−ジビニルジシロキサンのマススペクトル測定結果である。4 is a mass spectrum measurement result of 1-methoxy-3-hydroxy-1,3-diisopropyl-1,3-divinyldisiloxane obtained in Example 5. FIG. 実施例５で得られた１，３−ジヒドロキシ−１，３−ジイソプロピル−１，３−ジビニルジシロキサンのマススペクトル測定結果である。4 is a mass spectrum measurement result of 1,3-dihydroxy-1,3-diisopropyl-1,3-divinyldisiloxane obtained in Example 5. FIG.

以下、本発明を実施例に基づいて更に具体的に説明するが、本発明はこれらに限定されるものではない。   EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these.

（実施例１）
［１，３−ジアルコキシジシロキサンの合成］
不活性雰囲気下、攪拌装置、温度計を備えた１００ｍＬの３つ口フラスコに、ジメトキシイソプロピルビニルシラン（一般式（１）の化合物）５．０ｇ（３１．４ｍｍｏｌ）とヘキサン２５ｍｌを仕込み、ドライアイス／エタノールにより内温を−１５℃に冷却した。硫酸３．１ｇ（３１．４ｍｍｏｌ）および水１．７ｇ（９４．４ｍｍｏｌ）を、内温を−１０℃以下に保ったまま滴下し、その後３０分間撹拌し、目的の１，３−ジメトキシ−１，３−ジイソプロピル−１，３−ジビニルジシロキサン、１−メトキシ−３−ヒドロキシ−１，３−ジイソプロピル−１，３−ジビニルジシロキサンおよび１，３−ジヒドロキシ−１，３−ジイソプロピル−１，３−ジビニルジシロキサン（一般式（２）の化合物）が生成していることをＧＣ／ＭＳ（ＥＩ）で確認した。反応液をＧＣ／ＭＳ（ＥＩ）で分析した結果は以下の通りであった。
１，３−ジメトキシ−１，３−ジイソプロピル−１，３−ジビニルジシロキサン（Ｃ１２Ｈ２６Ｏ３Ｓｉ２） ｍ／ｚ：２３１（イソプロピル基脱離）、
１−メトキシ−３−ヒドロキシ−１，３−ジイソプロピル−１，３−ジビニルジシロキサン（Ｃ１１Ｈ２４Ｏ３Ｓｉ２） ｍ／ｚ：２１７（イソプロピル基脱離）、
１，３−ジヒドロキシ−１，３−ジイソプロピル−１，３−ジビニルジシロキサン（Ｃ１０Ｈ２２Ｏ３Ｓｉ２） ｍ／ｚ：２０３（イソプロピル基脱離）
１，３−ジメトキシ−１，３−ジイソプロピル−１，３−ジビニルジシロキサン、１−メトキシ−３−ヒドロキシ−１，３−ジイソプロピル−１，３−ジビニルジシロキサンおよび１，３−ジヒドロキシ−１，３−ジイソプロピル−１，３−ジビニルジシロキサンは単離せず、次工程へ進んだ。 Example 1
[Synthesis of 1,3-dialkoxydisiloxane]
Under an inert atmosphere, a 100 mL three-necked flask equipped with a stirrer and a thermometer was charged with 5.0 g (31.4 mmol) of dimethoxyisopropylvinylsilane (compound of general formula (1)) and 25 ml of hexane, and dried ice / The internal temperature was cooled to -15 ° C with ethanol. 3.1 g (31.4 mmol) of sulfuric acid and 1.7 g (94.4 mmol) of water were added dropwise while maintaining the internal temperature at −10 ° C. or lower, and then stirred for 30 minutes to obtain the desired 1,3-dimethoxy-1 , 3-Diisopropyl-1,3-divinyldisiloxane, 1-methoxy-3-hydroxy-1,3-diisopropyl-1,3-divinyldisiloxane and 1,3-dihydroxy-1,3-diisopropyl-1,3 -It confirmed with GC / MS (EI) that the divinyl disiloxane (compound of General formula (2)) was producing | generating. The result of analyzing the reaction solution by GC / MS (EI) was as follows.
1,3-dimethoxy-1,3-diisopropyl-1,3-divinyldisiloxane (C 12 H 26 O 3 Si 2 ) m / z: 231 (isopropyl group elimination),
1-methoxy-3-hydroxy-1,3-diisopropyl-1,3-divinyldisiloxane (C 11 H 24 O 3 Si 2 ) m / z: 217 (isopropyl group elimination),
1,3-dihydroxy-1,3-diisopropyl-1,3-divinyldisiloxane (C 10 H 22 O 3 Si 2 ) m / z: 203 (isopropyl group elimination)
1,3-dimethoxy-1,3-diisopropyl-1,3-divinyldisiloxane, 1-methoxy-3-hydroxy-1,3-diisopropyl-1,3-divinyldisiloxane and 1,3-dihydroxy-1, The 3-diisopropyl-1,3-divinyldisiloxane was not isolated and proceeded to the next step.

［シクロテトラシロキサンの合成］
上記反応液を分層して水層を除去したのち、硫酸１．５ｇ（０．１６ｍｏｌ）を加え、還流条件で１時間撹拌した。反応終了後、硫酸層を除去し、得られた有機層を炭酸水素ナトリウム水溶液で中和し硫酸マグネシウムで乾燥した。ロータリーエバポレーターで溶媒留去したのち、減圧蒸留にて目的の２，４，６，８−テトライソプロピル−２，４，６，８−テトラビニルシクロテトラシロキサン（一般式（３）の化合物）が主成分（ＧＣ面積％：５４．０％）の液体が２．６ｇ（２，４，６，８−テトライソプロピル−２，４，６，８−テトラビニルシクロテトラシロキサンの収量：１．４ｇ＝２．６ｇ×０．５４）得られた。一般式（３）の化合物の収率は３９．７％であった。この蒸留精製物をＧＣ／ＭＳ（ＥＩ）で分析した結果は以下の通りであった。 [Synthesis of cyclotetrasiloxane]
After separating the reaction solution and removing the aqueous layer, 1.5 g (0.16 mol) of sulfuric acid was added, and the mixture was stirred for 1 hour under reflux conditions. After completion of the reaction, the sulfuric acid layer was removed, and the obtained organic layer was neutralized with an aqueous sodium hydrogen carbonate solution and dried over magnesium sulfate. After distilling off the solvent with a rotary evaporator, the desired 2,4,6,8-tetraisopropyl-2,4,6,8-tetravinylcyclotetrasiloxane (compound of general formula (3)) is mainly produced by distillation under reduced pressure. 2.6 g of liquid of component (GC area%: 54.0%) (yield of 2,4,6,8-tetraisopropyl-2,4,6,8-tetravinylcyclotetrasiloxane: 1.4 g = 2) .6 g × 0.54). The yield of the compound of general formula (3) was 39.7%. The results of analysis of this distilled and purified product by GC / MS (EI) were as follows.

２，４，６，８−テトライソプロピル−２，４，６，８−テトラビニルシクロテトラシロキサン（Ｃ２０Ｈ４０Ｏ４Ｓｉ４） ｍ／ｚ：３７０（イソプロピル基２個脱離）
（比較例１）
実施例１において、シクロテトラシロキサンの合成工程で分層・水層除去作業を行わないこと以外は、実施例１と同様の実験を行った。蒸留精製物（液体）は、収量２．６ｇ、目的の２，４，６，８−テトライソプロピル−２，４，６，８−テトラビニルシクロテトラシロキサンは、ＧＣ面積％が２．４％であり、極微量しか（２．６ｇ×０．０２４＝０．０６２ｇ、収率１．７％）生成しなかった。 2,4,6,8 tetraisopropyl 2,4,6,8 tetravinylcyclotetrasiloxane (C 20 H 40 O 4 Si 4) m / z: 370 (2 pieces leaving isopropyl)
(Comparative Example 1)
In Example 1, the same experiment as in Example 1 was performed except that the separation / aqueous layer removal operation was not performed in the cyclotetrasiloxane synthesis step. Distilled purified product (liquid) has a yield of 2.6 g, and the desired 2,4,6,8-tetraisopropyl-2,4,6,8-tetravinylcyclotetrasiloxane has a GC area percentage of 2.4%. There was only a very small amount (2.6 g × 0.024 = 0.062 g, yield 1.7%).

（実施例２）
［シクロテトラシロキサン選択率の向上］
実施例１において、シクロテトラシロキサンの合成工程での反応を、還流条件で６時間撹拌に変更した以外は、実施例１と同様の実験を行った。目的の２，４，６，８−テトライソプロピル−２，４，６，８−テトラビニルシクロテトラシロキサンへの転換率の経時変化をＧＣ分析により確認した。反応終了後、実施例１と同様に処理を行った。一般式（３）の化合物の収率は６９．２％であった。結果を図１および図２に示す。 (Example 2)
[Improvement of cyclotetrasiloxane selectivity]
In Example 1, the same experiment as in Example 1 was performed except that the reaction in the synthesis process of cyclotetrasiloxane was changed to stirring for 6 hours under reflux conditions. The time-dependent change in the conversion rate to the desired 2,4,6,8-tetraisopropyl-2,4,6,8-tetravinylcyclotetrasiloxane was confirmed by GC analysis. After completion of the reaction, the same treatment as in Example 1 was performed. The yield of the compound of general formula (3) was 69.2%. The results are shown in FIG. 1 and FIG.

（実施例３）
［シクロテトラシロキサン選択率の向上、室温（２５℃）１ヶ月（７２０時間）］
実施例１において、シクロテトラシロキサンの合成工程での反応を、還流条件で３０分撹拌後さらに室温で１ヶ月撹拌に変更した以外は、実施例１と同様の実験を行った。目的の２，４，６，８−テトライソプロピル−２，４，６，８−テトラビニルシクロテトラシロキサンへの転換率の経時変化をＧＣ分析により確認した。反応終了後、実施例１と同様に処理を行った。一般式（３）の化合物の収率は７７．０％であった。結果を図３および図４に示す。 (Example 3)
[Improvement of cyclotetrasiloxane selectivity, room temperature (25 ° C.) 1 month (720 hours)]
The same experiment as in Example 1 was performed except that the reaction in the synthesis process of cyclotetrasiloxane in Example 1 was changed to stirring for 1 month at room temperature after stirring for 30 minutes under reflux conditions. The time-dependent change in the conversion rate to the desired 2,4,6,8-tetraisopropyl-2,4,6,8-tetravinylcyclotetrasiloxane was confirmed by GC analysis. After completion of the reaction, the same treatment as in Example 1 was performed. The yield of the compound of general formula (3) was 77.0%. The results are shown in FIG. 3 and FIG.

（実施例４）
［２，４，６，８−テトライソプロピル−２，４，６，８−テトラビニルシクロテトラシロキサンを用いた絶縁膜の製造］
実施例１で得た２，４，６，８−テトライソプロピル−２，４，６，８−テトラビニルシクロテトラシロキサン（一般式（３）の化合物）が主成分の液体を蒸留精製した２，４，６，８−テトライソプロピル−２，４，６，８−テトラビニルシクロテトラシロキサンを原料として、図５の装置を用いて、原料温度１２０℃、キャリアガス（Ｈｅ）流量１００ｓｃｃｍ、原料容器内圧力２２Ｔｏｒｒ、基板温度１５０℃、反応室内圧力１００Ｐａで、電源周波数１３．５６ＭＨｚのＲＦ電源の出力を２５Ｗに設定したＰＥＣＶＤ法により、Ｓｉ基板上に２分成膜を行った。成膜した絶縁膜について日本分光株式会社製のエリプソメーター（型式：ＭＥＬ−３０Ｓ）を用いて膜厚を測定したところ約１５０ｎｍであった。この絶縁膜上に、アルミ電極を蒸着法によって成膜した後、Ａｇｉｌｅｎｔ社製の４２８４ＡプレシジョンＬＣＲメータにより２５℃、周波数１ｋＨｚの静電容量と誘電損失を測定し、比誘電率を計算したところ、ｋ ２．６９、ｔａｎδ＝０．０００４であった。測定部分の誘電体の面積は１．０１×１０−８ｍ２であった。また、直流電流＋４０Ｖの条件でのリーク電流を測定したところ、８．８×１０−１０Ａ／ｃｍ２の電流密度であった。 Example 4
[Production of insulating film using 2,4,6,8-tetraisopropyl-2,4,6,8-tetravinylcyclotetrasiloxane]
2,4,6,8-tetraisopropyl-2,4,6,8-tetravinylcyclotetrasiloxane (compound of general formula (3)) obtained in Example 1 was purified by distillation. Using 4,6,8-tetraisopropyl-2,4,6,8-tetravinylcyclotetrasiloxane as a raw material, using the apparatus of FIG. A film was formed on the Si substrate for 2 minutes by PECVD with a pressure of 22 Torr, a substrate temperature of 150 ° C., a reaction chamber pressure of 100 Pa, and an output of an RF power supply with a power supply frequency of 13.56 MHz set to 25 W. When the film thickness of the formed insulating film was measured using an ellipsometer (model: MEL-30S) manufactured by JASCO Corporation, it was about 150 nm. After forming an aluminum electrode on this insulating film by vapor deposition, the capacitance and dielectric loss at 25 ° C. and a frequency of 1 kHz were measured with an Agilent 4284A Precision LCR meter, and the relative dielectric constant was calculated. k 2.69 and tan δ = 0.0004. The area of the dielectric in the measurement part was 1.01 × 10 −8 m 2 . Further, when the leakage current was measured under the condition of DC current + 40V, the current density was 8.8 × 10 −10 A / cm 2 .

（実施例５）
［１，３−ジメトキシ−１，３−ジイソプロピル−１，３−ジビニルジシロキサン、１−メトキシ−３−ヒドロキシ−１，３−ジイソプロピル−１，３−ジビニルジシロキサンおよび１，３−ジヒドロキシ−１，３−ジイソプロピル−１，３−ジビニルジシロキサンの合成］
不活性雰囲気下、攪拌装置、温度計を備えた２００ｍＬの３つ口フラスコに、ジメトキシイソプロピルビニルシラン１５．０ｇ（９３．６ｍｍｏｌ）、ヘキサン９０ｍｌを仕込み、ドライアイス／エタノールにより内温を−２０℃に冷却した。硫酸０．９７ｇ（９．９ｍｍｏｌ）を添加し、水３．５１ｇ（１９５ｍｍｏｌ）を内温−１５℃以下に保ち３０分かけて滴下した。内温を−１０℃に保持したまま５時間撹拌後、トリエチルアミン２．７ｇ（２６．７ｍｍｏｌ）を添加し、水層を除去し有機層を硫酸マグネシウムで乾燥した。ろ過後、ロータリーエバポレーターで溶媒留去したのち、減圧蒸留にて目的の１，３−ジメトキシ−１，３−ジイソプロピル−１，３−ジビニルジシロキサン、１−メトキシ−３−ヒドロキシ−１，３−ジイソプロピル−１，３−ジビニルジシロキサンおよび１，３−ジヒドロキシ−１，３−ジイソプロピル−１，３−ジビニルジシロキサンの混合物である液体２．７ｇが得られた。この混合物をシリカゲルカラムクロマトグラフィー（溶出溶媒：ヘキサン／酢酸エチル＝９／１）により精製し、目的化合物である１，３−ジメトキシ−１，３−ジイソプロピル−１，３−ジビニルジシロキサンを０．５１ｇ、収率４．０％、１−メトキシ−３−ヒドロキシ−１，３−ジイソプロピル−１，３−ジビニルジシロキサンを１．７８ｇ、収率１４．６％、１，３−ジヒドロキシ−１，３−ジイソプロピル−１，３−ジビニルジシロキサンを０．３１ｇ、収率２．７％で得た。それぞれの化合物をＧＣ／ＭＳ（ＥＩ）（図６−８）および１Ｈ−ＮＭＲで分析した結果は以下の通りであった。 (Example 5)
[1,3-dimethoxy-1,3-diisopropyl-1,3-divinyldisiloxane, 1-methoxy-3-hydroxy-1,3-diisopropyl-1,3-divinyldisiloxane and 1,3-dihydroxy-1 Of 3,3-diisopropyl-1,3-divinyldisiloxane]
In an inert atmosphere, a 200 mL three-necked flask equipped with a stirrer and a thermometer was charged with 15.0 g (93.6 mmol) of dimethoxyisopropylvinylsilane and 90 ml of hexane, and the internal temperature was adjusted to −20 ° C. with dry ice / ethanol. Cooled down. 0.97 g (9.9 mmol) of sulfuric acid was added, and 3.51 g (195 mmol) of water was added dropwise over 30 minutes while maintaining the internal temperature at −15 ° C. or lower. After stirring for 5 hours while maintaining the internal temperature at −10 ° C., 2.7 g (26.7 mmol) of triethylamine was added, the aqueous layer was removed, and the organic layer was dried over magnesium sulfate. After filtration, the solvent was distilled off with a rotary evaporator, and then the desired 1,3-dimethoxy-1,3-diisopropyl-1,3-divinyldisiloxane, 1-methoxy-3-hydroxy-1,3- There were obtained 2.7 g of a liquid which was a mixture of diisopropyl-1,3-divinyldisiloxane and 1,3-dihydroxy-1,3-diisopropyl-1,3-divinyldisiloxane. This mixture was purified by silica gel column chromatography (eluent: hexane / ethyl acetate = 9/1), and 1,3-dimethoxy-1,3-diisopropyl-1,3-divinyldisiloxane, which is the target compound, was reduced to a concentration of 0. 51 g, 4.0% yield, 1.78 g 1-methoxy-3-hydroxy-1,3-diisopropyl-1,3-divinyldisiloxane, 14.6% yield, 1,3-dihydroxy-1, 0.31 g of 3-diisopropyl-1,3-divinyldisiloxane was obtained with a yield of 2.7%. The result of having analyzed each compound by GC / MS (EI) (FIGS. 6-8) and 1 H-NMR was as follows.

ＧＣ／ＭＳ（ＥＩ）
１，３−ジメトキシ−１，３−ジイソプロピル−１，３−ジビニルジシロキサン（Ｃ１２Ｈ２６Ｏ３Ｓｉ２） ｍ／ｚ：２３１（イソプロピル基脱離）
１−メトキシ−３−ヒドロキシ−１，３−ジイソプロピル−１，３−ジビニルジシロキサン（Ｃ１１Ｈ２４Ｏ３Ｓｉ２） ｍ／ｚ：２１７（イソプロピル基脱離）
１，３−ジヒドロキシ−１，３−ジイソプロピル−１，３−ジビニルジシロキサン（Ｃ１０Ｈ２２Ｏ３Ｓｉ２） ｍ／ｚ：２０３（イソプロピル基脱離）
１Ｈ−ＮＭＲ（５００ＭＨｚ，ＣＤＣｌ３，δｐｐｍ）
１，３−ジヒドロキシ−１，３−ジイソプロピル−１，３−ジビニルジシロキサン
６．１３−５．９２（ｍ，６Ｈ）、３．５３（ｓ，６Ｈ）、１．０１（ｄ，Ｊ＝６．５Ｈｚ，１２Ｈ）、０．９４−０．８７（ｍ，２Ｈ）
１−メトキシ−３−ヒドロキシ−１，３−ジイソプロピル−１，３−ジビニルジシロキサン
６．１３−５．９０（ｍ，６Ｈ）、３．５２（ｓ，３Ｈ）、２．３１（ｓ,１Ｈ）、１．００（ｄｄ，Ｊ＝６Ｈｚ，Ｊ＝２．５Ｈｚ，６Ｈ）、１．０３（ｄ，Ｊ＝６Ｈｚ，６Ｈ）、０．９６−０．８８（ｍ，２Ｈ）
１，３−ジヒドロキシ−１，３−ジイソプロピル−１，３−ジビニルジシロキサン
６．１０−５．９１（ｍ，６Ｈ）、２．４０（ｓ，２Ｈ）、１．０１（ｄ，Ｊ＝７．５Ｈｚ，１２Ｈ）、０．９７−０．８９（ｍ，２Ｈ）
（参考例１）
［２，４，６−トリイソプロピル−２，４，６−トリビニルシクロトリシロキサンを用いた絶縁膜の製造］
２，４，６−トリイソプロピル−２，４，６−トリビニルシクロトリシロキサンを原料として、図５の装置を用いて、原料温度８３℃、キャリアガス（Ｈｅ）流量１００ｓｃｃｍ、原料容器内圧力２２Ｔｏｒｒ、基板温度１５０℃、反応室内圧力１００Ｐａで、電源周波数１３．５６ＭＨｚのＲＦ電源の出力を２５Ｗに設定したＰＥＣＶＤ法により、Ｓｉ基板上に３分成膜を行った。成膜した絶縁膜について日本分光株式会社製のエリプソメーター（型式：ＭＥＬ−３０Ｓ）を用いて膜厚を測定したところ約２１０ｎｍであった。この絶縁膜上に、アルミ電極を蒸着法によって成膜した後、Ａｇｉｌｅｎｔ社製の４２８４ＡプレシジョンＬＣＲメータにより２５℃、周波数１ｋＨｚの静電容量と誘電損失を測定し、比誘電率を計算したところ、ｋ ２．７４、ｔａｎδ＝０．０１であった。測定部分の誘電体の面積は９．８８×１０−７ｍ２であった。また、直流電流＋４０Ｖの条件でのリーク電流を測定したところ、２．０×１０−９Ａ／ｃｍ２の電流密度であった。 GC / MS (EI)
1,3-dimethoxy-1,3-diisopropyl-1,3-divinyldisiloxane (C 12 H 26 O 3 Si 2 ) m / z: 231 (isopropyl group elimination)
1-methoxy-3-hydroxy-1,3-diisopropyl-1,3-divinyldisiloxane (C 11 H 24 O 3 Si 2 ) m / z: 217 (isolation of isopropyl group)
1,3-dihydroxy-1,3-diisopropyl-1,3-divinyldisiloxane (C 10 H 22 O 3 Si 2 ) m / z: 203 (isopropyl group elimination)
1 H-NMR (500 MHz, CDCl 3 , δ ppm)
1,3-dihydroxy-1,3-diisopropyl-1,3-divinyldisiloxane 6.13-5.92 (m, 6H), 3.53 (s, 6H), 1.01 (d, J = 6 .5Hz, 12H), 0.94-0.87 (m, 2H)
1-methoxy-3-hydroxy-1,3-diisopropyl-1,3-divinyldisiloxane 6.13-5.90 (m, 6H), 3.52 (s, 3H), 2.31 (s, 1H ), 1.00 (dd, J = 6 Hz, J = 2.5 Hz, 6H), 1.03 (d, J = 6 Hz, 6H), 0.96-0.88 (m, 2H)
1,3-dihydroxy-1,3-diisopropyl-1,3-divinyldisiloxane 6.10-5.91 (m, 6H), 2.40 (s, 2H), 1.01 (d, J = 7 .5Hz, 12H), 0.97-0.89 (m, 2H)
(Reference Example 1)
[Production of insulating film using 2,4,6-triisopropyl-2,4,6-trivinylcyclotrisiloxane]
Using 2,4,6-triisopropyl-2,4,6-trivinylcyclotrisiloxane as a raw material, using the apparatus of FIG. 5, the raw material temperature is 83 ° C., the carrier gas (He) flow rate is 100 sccm, and the raw material container pressure is 22 Torr. A film was formed on the Si substrate for 3 minutes by PECVD with a substrate temperature of 150 ° C., a reaction chamber pressure of 100 Pa, and an RF power output of 13.56 MHz set to 25 W. When the film thickness of the formed insulating film was measured using an ellipsometer (model: MEL-30S) manufactured by JASCO Corporation, it was about 210 nm. After forming an aluminum electrode on this insulating film by vapor deposition, the capacitance and dielectric loss at 25 ° C. and a frequency of 1 kHz were measured with an Agilent 4284A Precision LCR meter, and the relative dielectric constant was calculated. k 2.74, tan δ = 0.01. The area of the dielectric in the measurement portion was 9.88 × 10 −7 m 2 . Further, when the leakage current was measured under the condition of direct current +40 V, it was a current density of 2.0 × 10 −9 A / cm 2 .

実施例４の環状８員環である２，４，６，８−テトライソプロピル−２，４，６，８−テトラビニルシクロテトラシロキサンからなる膜は、参考例１の環状６員環である２，４，６−トリイソプロピル−２，４，６−トリビニルシクロトリシロキサンからなる膜よりも、よりｋ値が小さく、絶縁膜として好適である。   A film made of 2,4,6,8-tetraisopropyl-2,4,6,8-tetravinylcyclotetrasiloxane, which is a cyclic 8-membered ring of Example 4, is a cyclic 6-membered ring of Reference Example 2 , 4,6-triisopropyl-2,4,6-trivinylcyclotrisiloxane has a smaller k value and is suitable as an insulating film.

１．ＰＥＣＶＤチャンバー
２．基板
３．上部電極
４．下部電極
５．恒温槽
６．原料容器
７．真空ポンプ
８．マッチング回路
９．ＲＦ電源
１０．アース
１１．ヒーター
１２．マスフローコントローラー
１３．ヘリウムガス 1. PECVD chamber Substrate 3. Upper electrode 4. Lower electrode 5. Thermostatic bath 6. 6. Raw material container Vacuum pump 8. 8. Matching circuit RF power supply 10. Earth 11. Heater 12. Mass flow controller 13. Helium gas

Claims (7)

下記一般式（１）
Figure 2014065699
 （式中、Ｒ１、Ｒ２は炭素数１〜３の直鎖または分岐鎖のアルキル基を示す。）で表されるジアルコキシアルキルビニルシラン化合物を、酸または塩基の共存下、水と反応させることにより、下記一般式（２）
Figure 2014065699
 （式中、Ｒ１は一般式（１）に同じ。Ｒ３、Ｒ４は一般式（１）のＲ２に同じかまたは水素原子を示す。）で表されるジシロキサン化合物を製造し、次いで、いったん水層を除去した後、一般式（２）で表されるジシロキサン化合物を酸または塩基の共存下、反応させることを特徴とする、下記一般式（３）
Figure 2014065699
 （式中、Ｒ１は一般式（１）に同じ。）で表される環状シロキサン化合物の製造方法。 The following general formula (1)
Figure 2014065699
 (Wherein R 1 and R 2 represent a linear or branched alkyl group having 1 to 3 carbon atoms), and the dialkoxyalkylvinylsilane compound represented by the above is reacted with water in the presence of an acid or a base. The following general formula (2)
Figure 2014065699
 (Wherein R 1 is the same as in general formula (1). R 3 and R 4 are the same as or in the hydrogen atom in R 2 of general formula (1)). Next, once the aqueous layer is removed, the disiloxane compound represented by the general formula (2) is reacted in the presence of an acid or a base, and the following general formula (3)
Figure 2014065699
 (Wherein R 1 is the same as in general formula (1)). 一般式（１）で表されるジアルコキシアルキルビニルシラン化合物を酸または塩基の共存下、水と反応させる際の反応温度が−５０〜２５℃であることを特徴とする請求項１に記載の製造方法。 2. The production according to claim 1, wherein the reaction temperature when the dialkoxyalkylvinylsilane compound represented by the general formula (1) is reacted with water in the presence of an acid or a base is -50 to 25 ° C. Method. 一般式（２）で表されるジシロキサン化合物を酸または塩基の共存下、反応させる反応時間が３０分（０．５時間）以上、１ヶ月（７２０時間）以下であることを特徴とする請求項１又は２に記載の製造方法。 A reaction time for reacting the disiloxane compound represented by the general formula (2) in the presence of an acid or a base is 30 minutes (0.5 hours) or longer and 1 month (720 hours) or shorter. Item 3. The method according to Item 1 or 2. 酸として硫酸の共存下に反応を行うことを特徴とする請求項１〜３のいずれかに記載の製造方法。 The process according to any one of claims 1 to 3, wherein the reaction is carried out in the presence of sulfuric acid as an acid. Ｒ１がイソプロピル基、Ｒ２がメチル基、Ｒ３およびＲ４がメチル基または水素原子であることを特徴とする請求項１〜４のいずれかに記載の製造方法。 The production method according to claim 1, wherein R 1 is an isopropyl group, R 2 is a methyl group, R 3 and R 4 are a methyl group or a hydrogen atom. 請求項１〜５のいずれかに記載の製造方法により製造された環状シロキサン化合物を材料として用いることを特徴とする絶縁膜。 An insulating film comprising a cyclic siloxane compound produced by the production method according to claim 1 as a material. 下記一般式（２）で表されることを特徴とするジシロキサン化合物。
Figure 2014065699
 （式中、Ｒ１は一般式（１）に同じ。Ｒ３、Ｒ４は一般式（１）のＲ２に同じかまたは水素原子を示す。） A disiloxane compound represented by the following general formula (2):
Figure 2014065699
 (In the formula, R 1 is the same as in general formula (1). R 3 and R 4 are the same as R 2 in general formula (1) or a hydrogen atom.)
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