JP6202179B2 - Disiloxane compound - Google Patents

Disiloxane compound Download PDF

Info

Publication number
JP6202179B2
JP6202179B2 JP2016213486A JP2016213486A JP6202179B2 JP 6202179 B2 JP6202179 B2 JP 6202179B2 JP 2016213486 A JP2016213486 A JP 2016213486A JP 2016213486 A JP2016213486 A JP 2016213486A JP 6202179 B2 JP6202179 B2 JP 6202179B2
Authority
JP
Japan
Prior art keywords
divinyldisiloxane
diisopropyl
general formula
hydroxy
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
JP2016213486A
Other languages
Japanese (ja)
Other versions
JP2017019872A (en
Inventor
哲平 早川
哲平 早川
和久 河野
和久 河野
洋一 千葉
洋一 千葉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tosoh Corp
Original Assignee
Tosoh Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tosoh Corp filed Critical Tosoh Corp
Publication of JP2017019872A publication Critical patent/JP2017019872A/en
Application granted granted Critical
Publication of JP6202179B2 publication Critical patent/JP6202179B2/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • 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
    • H01L21/02205—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—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]

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Power Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Plasma & Fusion (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Spectroscopy & Molecular Physics (AREA)

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（２）で表されることを特徴とするジシロキサン化合物。 That is, the present invention is as follows.
[1] A disiloxane compound represented by the following general formula (2).

Figure 0006202179
（式中、Ｒ１はエチル基、ノルマルプロピル基、イソプロピル基であり、Ｒ３、Ｒ４は炭素数１〜３の直鎖または分岐鎖のアルキル基若しくは水素原子を示す。）
［２］Ｒ１がイソプロピル基であることを特徴とする上述の［１］に記載のジシロキサン化合物。
Figure 0006202179
 (In the formula, R 1 represents an ethyl group, a normal propyl group, or an isopropyl group, and R 3 and R 4 represent a linear or branched alkyl group having 1 to 3 carbon atoms or a hydrogen atom.)
[2] The disiloxane compound as described in [1] above, wherein R 1 is an isopropyl group.

以下、本発明をさらに詳細に説明する。   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 0006202179
（式中、Ｒ１はエチル基、ノルマルプロピル基、イソプロピル基であり、Ｒ３、Ｒ４は炭素数１〜３の直鎖または分岐鎖のアルキル基若しくは水素原子を示す。）
一般式（２）におけるＲ１はエチル基、ノルマルプロピル基、イソプロピル基であり、Ｒ３、Ｒ４は炭素数１〜３の直鎖または分岐鎖のアルキル基若しくは水素原子を示し、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。
Figure 0006202179
 (In the formula, R 1 represents an ethyl group, a normal propyl group, or an isopropyl group, and R 3 and R 4 represent a linear or branched alkyl group having 1 to 3 carbon atoms or a hydrogen atom.)
R 1 in the general formula (2) is an ethyl group, a normal propyl group, or an isopropyl group, and R 3 and R 4 each represent a linear or branched alkyl group having 1 to 3 carbon atoms or a hydrogen atom, preferably R 1 1 is an isopropyl group, and 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 0006202179
（式中、Ｒ１はエチル基、ノルマルプロピル基、イソプロピル基を示す。）
一般式（３）におけるＲ１はエチル基、ノルマルプロピル基、イソプロピル基であり、好ましくはＲ１がイソプロピル基である。
Figure 0006202179
 (In the formula, R 1 represents an ethyl group, a normal propyl group, or an isopropyl group.)
R 1 in the general formula (3) is an ethyl group, a normal propyl group, or an isopropyl group, 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 producing the insulating film, for example, a thin film can be produced on the substrate 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, but the coating method, the heating method, and a combination thereof are particularly limited. 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 (2)

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 0006202179
 （式中、Ｒ１はエチル基、ノルマルプロピル基、イソプロピル基であり、Ｒ３、Ｒ４は炭素数１〜３の直鎖または分岐鎖のアルキル基若しくは水素原子を示す。） A disiloxane compound represented by the following general formula (2):
Figure 0006202179
 (In the formula, R 1 represents an ethyl group, a normal propyl group, or an isopropyl group, and R 3 and R 4 represent a linear or branched alkyl group having 1 to 3 carbon atoms or a hydrogen atom.) Ｒ１がイソプロピル基であることを特徴とする請求項１に記載のジシロキサン化合物。 The disiloxane compound according to claim 1, wherein R 1 is an isopropyl group.
JP2016213486A 2011-12-22 2016-10-31 Disiloxane compound Active JP6202179B2 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2011281382 2011-12-22
JP2011281382 2011-12-22
JP2012198615 2012-09-10
JP2012198615 2012-09-10

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
JP2012252735A Division JP6131575B2 (en) 2011-12-22 2012-11-16 Method for producing cyclic siloxane compound and disiloxane compound

Publications (2)

Publication Number Publication Date
JP2017019872A JP2017019872A (en) 2017-01-26
JP6202179B2 true JP6202179B2 (en) 2017-09-27

Family

ID=48668318

Family Applications (2)

Application Number Title Priority Date Filing Date
JP2012252735A Active JP6131575B2 (en) 2011-12-22 2012-11-16 Method for producing cyclic siloxane compound and disiloxane compound
JP2016213486A Active JP6202179B2 (en) 2011-12-22 2016-10-31 Disiloxane compound

Family Applications Before (1)

Application Number Title Priority Date Filing Date
JP2012252735A Active JP6131575B2 (en) 2011-12-22 2012-11-16 Method for producing cyclic siloxane compound and disiloxane compound

Country Status (3)

Country Link
JP (2) JP6131575B2 (en)
TW (1) TW201341393A (en)
WO (1) WO2013094421A1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10941254B2 (en) 2017-01-18 2021-03-09 Sumitomo Chemical Company, Limited Molded article and method of producing the same
JP7475578B2 (en) 2020-07-01 2024-04-30 信越化学工業株式会社 Method for producing 1,3-dihydroxy-1,1,3,3-tetra-tert-butoxydisiloxane

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE793513A (en) * 1971-12-30 1973-06-29 Stauffer Chemical Co Alcoxysiloxanols
US3763212A (en) * 1972-02-04 1973-10-02 Gen Electric Hydrolysis of alkylalkenyldichlorosilane
JPS538701B2 (en) * 1973-03-31 1978-03-31
JPH07285974A (en) * 1994-04-18 1995-10-31 Shin Etsu Chem Co Ltd Production of cyclotetrasiloxane
JP3079939B2 (en) * 1994-08-25 2000-08-21 信越化学工業株式会社 Method for producing low molecular weight organosiloxane having silanol group
JP3252642B2 (en) * 1995-03-06 2002-02-04 信越化学工業株式会社 Method for producing low molecular weight organosilane or siloxane having silanol group
JP3206384B2 (en) * 1995-08-01 2001-09-10 信越化学工業株式会社 Method for producing alkoxysiloxane
US6037092A (en) * 1999-08-17 2000-03-14 Xerox Corporation Stabilized fluorosilicone fuser members
JP3497812B2 (en) * 2000-10-30 2004-02-16 株式会社デンソー Non-aqueous electrolyte secondary battery using non-aqueous electrolyte
JP4438385B2 (en) * 2002-11-28 2010-03-24 東ソー株式会社 Insulating film material, organosilane compound manufacturing method, insulating film, and semiconductor device using the same
JP2005097443A (en) * 2003-09-25 2005-04-14 Jsr Corp Method for producing film-forming composition, film-forming composition and insulated film-forming material
JP2005120355A (en) * 2003-09-25 2005-05-12 Jsr Corp Composition for forming film, method for forming film, and silica-based film
JP2005120354A (en) * 2003-09-25 2005-05-12 Jsr Corp Manufacturing method of composition for forming film, composition for forming film, and material for forming insulating film
US8790785B2 (en) * 2006-07-21 2014-07-29 Renesas Electronics Corporation Method of forming a porous insulation film
JP2008274365A (en) * 2007-05-01 2008-11-13 Shin Etsu Chem Co Ltd MATERIAL FOR FORMING Si-CONTAINING FILM, Si-CONTAINING FILM, MANUFACTURING METHOD THEREFOR, AND SEMICONDUCTOR DEVICE

Also Published As

Publication number Publication date
JP2014065699A (en) 2014-04-17
JP6131575B2 (en) 2017-05-24
TW201341393A (en) 2013-10-16
WO2013094421A1 (en) 2013-06-27
JP2017019872A (en) 2017-01-26

Similar Documents

Publication Publication Date Title
US6572923B2 (en) Asymmetric organocyclosiloxanes and their use for making organosilicon polymer low-k dielectric film
US6440876B1 (en) Low-K dielectric constant CVD precursors formed of cyclic siloxanes having in-ring SI—O—C, and uses thereof
JP5353845B2 (en) Cyclic siloxane compound
JP4518421B2 (en) Method for producing low-k dielectric film
JP2008274365A (en) MATERIAL FOR FORMING Si-CONTAINING FILM, Si-CONTAINING FILM, MANUFACTURING METHOD THEREFOR, AND SEMICONDUCTOR DEVICE
WO2012144480A1 (en) Siloxane compound and cured product thereof
WO2009119583A1 (en) Material for chemical vapor deposition, silicon-containing insulating film and process for production thereof
JP6202179B2 (en) Disiloxane compound
JP2017511308A (en) Organic germanium amine compound and thin film deposition method using the same
JP4957037B2 (en) Organosilane compound, Si-containing film-forming material containing the same, production method and use
KR20200068734A (en) Aromatic amino siloxane functionalized material for use in capping porous dielectrics
JP5019742B2 (en) Cyclic siloxane compound, Si-containing film forming material, and use thereof
JP4479190B2 (en) Insulating film material comprising alkenyl group-containing organosilane compound, insulating film and semiconductor device using the same
JP4333480B2 (en) Si-containing film forming material and use thereof
TWI707861B (en) Method for producing silicon compound, and silicon compound
JP2011153213A (en) Method for producing cage silsesquioxane compound
JP5040162B2 (en) Si-containing film forming material comprising alkenyl group-containing organosilane compound and use thereof
JP2018172321A (en) Cyclic siloxane compound, production method thereof, method of producing electric insulating film using the same, and film
TWI849595B (en) Precursor for low-k silicon-containing film deposition, deposition method of low-k silicon-containing film and semiconductor device of the same
JP2011116758A (en) ORGANOSILANE COMPOUND, METHOD FOR PRODUCING THE SAME, Si-CONTAINING FILM-FORMING MATERIAL CONTAINING THE SAME AND METHOD FOR FORMING FILM
KR20230086947A (en) Precursor for low-k silicon-containing film deposition, deposition method of low-k silicon-containing film and semiconductor device of the same
JP4259217B2 (en) Insulating film material comprising an ester group-containing organosilane compound and insulating film using the same
KR20150108664A (en) precursor compounds and thin film deposition method using the precusor compoumds
TW202436311A (en) Cyclosilazane precursors and related methods
KR20150110311A (en) composition comprising boron-containing compound, boron-containing thin film and method for manufacturing boron-containing thin film

Legal Events

Date Code Title Description
A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20161104

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20170801

A977 Report on retrieval

Free format text: JAPANESE INTERMEDIATE CODE: A971007

Effective date: 20170803

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20170814

R151 Written notification of patent or utility model registration

Ref document number: 6202179

Country of ref document: JP

Free format text: JAPANESE INTERMEDIATE CODE: R151